Process for dyeing keratin hair fibres comprising application of specific composition T and application of (poly) carbodiimide compound and colorant

Abstract

The present invention relates to a process for dyeing keratin hair fibres, comprising: a) applying to the keratin hair fibres at least one composition T, the composition comprises at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; and then b) applying to the keratin hair fibres at least one composition C comprising:-at least one (poly) carbodiimide compound of formula (II); and-at least one colorant selected from the group consisting of pigments, direct dyes and mixtures thereof.

Description

[0001] The present invention relates to a method for dyeing keratinous hair fibers, which method comprises applying a specific composition T to the keratinous hair fibers, and subsequently applying a composition C comprising a (poly)carbodiimide compound and a colorant. Field of the Invention

[0002] In the field of dyeing keratinous hair fibers, it is known practice to dye keratinous hair fibers by various techniques using direct dyes or pigments for non-permanent coloring, or dye precursors for permanent coloring.

[0003] Basically, there are three types of methods for dyeing keratinous hair fibers:

[0004] a) “Permanent” dyeing, which functions to provide a substantial change to the natural color and uses oxidation dyes that penetrate into the keratinous hair fibers and form the dyeing by an oxidation condensation process;

[0005] b) Non-permanent, semi-permanent or direct dyeing, which does not use an oxidation condensation process and resists four or five shampoo washings; it consists of dyeing the keratin fibers with a dye composition containing direct dyes;

[0006] c) Temporary dyeing, which causes a change in the natural color of the keratinous hair fibers that is retained from one shampoo washing to the next, and is used to enhance or correct the tones already obtained. It can also be compared to a “cosmetic” process.

[0007] Another dyeing method involves the use of pigments. Specifically, the use of pigments on the surface of keratin fibers generally makes it possible to obtain a coloring visible on dark keratinous hair fibers, since the surface pigments mask the natural color of the fibers. However, the coloring obtained by this dyeing method has the disadvantage of having poor tolerance to shampoo washings and also to external agents such as sebum, sweat, brushing and / or friction.

[0008] Therefore, there is still a need for a method for dyeing keratinous hair fibers that has the following advantages: obtaining a uniform coloring coating on the keratinous hair fibers while forming a coating that is durable relative to shampoo washings and the various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without damaging the cosmetic properties of the keratinous hair fibers.

[0009] Therefore, the object of the present invention is to develop a method for dyeing keratinous hair fibers that has the following advantages: obtaining a smooth and uniform coloring coating on the keratinous hair fibers while forming a coating that is durable relative to shampoo washings and the various stresses (such as brushing and / or friction) that the keratinous hair fibers may undergo, without damaging the keratinous hair fibers. Summary of the Invention

[0010] Thus, one subject of the present invention is a method for dyeing keratinous hair fibers, the method comprising:

[0011] a) applying to the keratinous hair fibers at least one composition T, which composition comprises at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; and then

[0012] b) applying to the keratinous hair fibers at least one composition C, which composition comprises:

[0013] - at least one (poly)carbodiimide compound selected from compounds of the following formula (II); and

[0014] - at least one colorant selected from pigments, direct dyes and mixtures thereof.

[0015] By means of the method for dyeing keratinous hair fibers according to the present invention, colored coatings are obtained on the keratinous hair fibers, which coatings make it possible to obtain a coloring visible on all types of keratinous hair fibers and lasting with respect to shampooing, while preserving the physical qualities of the keratinous hair fibers. Such coatings can withstand the external stresses that the keratinous hair fibers may undergo, such as blow-drying and sweating. The coatings make it possible in particular to obtain a uniform deposit.

[0016] For the purposes of the present invention, the term "coloring lasting with respect to shampooing" means that the coloring obtained is lasting after one shampooing, preferably after five shampooings.

[0017] The term "at least one" means one or more.

[0018] Unless otherwise indicated, the limits of a range of values are included in the range, especially in the expressions "between... and" and "ranging from... to...".

[0019] The present invention is not limited to the examples shown. The features of the different examples can in particular be combined in variants not shown.

[0020] For the purposes of the present invention and unless otherwise indicated:

[0021] - "alkyl" denotes a straight-chain or branched-chain saturated group containing, for example, from 1 to 20 carbon atoms;

[0022] - "aminoalkyl" denotes an alkyl as previously defined, which alkyl contains an NH2 group;

[0023] - "hydroxyalkyl" denotes an alkyl as previously defined, which alkyl contains an OH group;

[0024] - "Alkylene" indicates a straight-chain or branched divalent saturated C2-C4 hydrocarbon-based group, such as methylene, ethylene or propylene;

[0025] - "Cycloalkyl" or "alicyclic alkyl" indicates a saturated monocyclic or polycyclic, preferably monocyclic, hydrocarbon-based group containing from 1 to 3 rings, preferably 2 rings and containing from 3 to 24 carbon atoms, particularly from 3 to 20 carbon atoms, more particularly from 3 to 13 carbon atoms, even more particularly from 3 to 12 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl, particularly cyclopropyl, cyclopentyl or cyclohexyl, it being understood that the cycloalkyl can be substituted by one or more (C1-C4) alkyls such as methyl; preferably, the cycloalkyl is isobornyl;

[0026] - "Cycloalkylene" indicates a divalent cycloalkyl, where "cycloalkyl" is as previously defined, preferably C3-C 12 ;

[0027] - "Aryl" is a monocyclic, bicyclic or tricyclic, fused or unfused, unsaturated and aromatic hydrocarbon-based cyclic group containing from 6 to 14 carbon atoms, preferably between 6 and 12 carbon atoms; preferably, the aryl contains 1 ring having 6 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthryl and biphenyl, it being understood that the aryl can be substituted by one or more (C1-C4) alkyls such as methyl, preferably tolyl, xylyl or methylnaphthyl; preferably, the aryl represents phenyl;

[0028] - "Arylene" is a divalent aryl, where "aryl" is as previously defined; preferably, the arylene represents phenylene;

[0029] - "Heterocyclic" group indicates a saturated or unsaturated, non-aromatic or aromatic, monocyclic or polycyclic hydrocarbon-based group containing one or more heteroatoms, preferably from 1 to 5 atoms selected from O, S or N, including from 3 to 20 ring members, preferably between 5 and 10 ring members, such as imidazolyl, pyrrolyl and furyl;

[0030] - "Heterocycloalkylene" is a divalent heterocyclic group, where "heterocyclic" is as previously defined;

[0031] - "Aryloxy" indicates aryl-oxy, where "aryl" is as previously defined;

[0032] - "Alkoxy" indicates alkyl-oxy, where "alkyl" is as previously defined;

[0033] - "Acetoxy" indicates an ester group R-C(O)-O-, where R is an alkyl as previously defined;

[0034] - A "reactive" group is a group that is capable of forming a covalent bond with another group, identical or different, through a chemical reaction.

[0035] Unless otherwise indicated, when a compound is referred to in this patent application, it also includes its optical isomers, its geometric isomers, its tautomers or its salts, either alone or as a mixture.

[0036] The term "(hair) keratin fiber" means a keratin hair fiber or hair. In other words, the expressions "(hair) keratin fiber", "keratin hair fiber" and "hair" are equivalent in the subsequent part of the specification.

[0037] For the purposes of the present invention, the term "keratin hair fiber" means a keratin hair fiber of the head. This term does not correspond to body hair, eyebrows or eyelashes.

[0038] For the purposes of the present invention, the term "silicone" means a compound containing at least one silicon atom, in particular a silicone polymer such as polydimethylsiloxane or amino-terminated polydimethylsiloxane.

[0039] Composition T

[0040] As shown above, the method according to the invention comprises a) applying to the keratin hair fibers at least one Composition T, which comprises at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of the composition.

[0041] Preferably, Composition T comprises a silicone content of less than or equal to 0.5% by weight relative to the total weight of the composition. More preferably, Composition T is silicone-free.

[0042] Composition T used in the context of the dyeing method according to the invention comprises at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant. The total amount of anionic surfactant and amphoteric surfactant is generally between 1% and 50% by weight relative to the total weight of Composition T.

[0043] Anionic surfactant

[0044] The term "anionic surfactant" means a surfactant comprising only anionic groups as ionic or ionizable groups.

[0045] In this specification, under the conditions of using the compositions of the invention (such as the medium or pH) and not containing any cationic charge, a substance is called "anionic" when it bears at least one permanent negative charge or when it can be ionized into a negatively charged substance.

[0046] Preferably, the anionic surfactant is selected from sulfate anionic surfactants.

[0047] For the purposes of the present invention, the term "sulfate anionic surfactant" means an anionic surfactant comprising one or more sulfate functional groups (-OSO3H or -OSO3 - ).

[0048] Such surfactants may advantageously be selected from alkyl sulfates, alkyl ether sulfates, alkyl amido sulfates, alkyl amido ether sulfates, alkyl aryl polyether sulfates, monoglyceride sulfates; and also their salts and mixtures thereof; the alkyl groups of these compounds particularly comprise from 8 to 30 carbon atoms, preferably from 8 to 26, and more preferably from 10 to 22 carbon atoms; the aryl group preferably denotes phenyl or benzyl; these compounds may be polyoxyalkyleneated, especially polyoxyethylenated, and preferably contain from 1 to 50 ethylene oxide units, and more preferably from 2 to 10 ethylene oxide units.

[0049] Preferably, the sulfate anionic surfactant is selected from:

[0050] - alkyl sulfates, especially C8 to C 26 and preferably C 10 to C 22 alkyl sulfates;

[0051] - alkyl ether sulfates, especially C8 to C 26 and preferably C 10 to C 22 alkyl ether sulfates, preferably containing from 2 to 10 ethylene oxide units;

[0052] Especially in the form of alkali metal salts, alkaline earth metal salts, ammonium salts or amino alcohol salts, and

[0053] their mixtures.

[0054] When the sulfate anionic surfactant is in salt form, the salt may be selected from alkali metal salts (such as sodium or potassium salts), ammonium salts, amine salts and especially amino alcohol salts and alkaline earth metal salts (such as magnesium salts), and mixtures thereof.

[0055] Examples of amino alcohol salts that may be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

[0056] Preferably, alkali metal salts or alkaline earth metal salts and especially sodium salts or magnesium salts are used.

[0057] Preferably, the sulfate anionic surfactant is selected from (C 10 -C 22 ) alkyl sulfates of sodium, triethanolamine, magnesium or ammonium, oxyethylenated (C 10 -C 22 ) alkyl ether sulfates of sodium, triethanolamine, ammonium or magnesium (e.g. with 1 or 2.2 moles of ethyleneoxy), and mixtures thereof.

[0058] Even better, the sulfate anionic surfactant is selected from (C 10 -C 22 ) alkyl sulfates of sodium, triethanolamine, ammonium or magnesium, or (C 10 -C 22 ) alkyl ether sulfates of sodium, triethanolamine, ammonium or magnesium, such as the compound with the INCI name sodium lauryl sulfate sold by BASF under the name Texapon Z95P, or the compound with the INCI name sodium laureth sulfate sold by BASF under the name Texapon N701.

[0059] Even more preferably, the sulfate anionic surfactant is selected from (C 10 -C 22 ) alkyl ether sulfates and their salts, especially (C 10 -C 22 ) alkyl ether sulfates of sodium, triethanolamine, ammonium or magnesium.

[0060] According to a preferred embodiment, the sulfate anionic surfactant is selected from sodium lauryl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, ammonium laureth sulfate and mixtures thereof, more preferably from sodium laureth sulfate.

[0061] Advantageously, the anionic surfactant is present in a total content ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight, and even more preferably from 12% to 20% by weight, relative to the total weight of composition T.

[0062] Amphoteric or zwitterionic surfactant

[0063] The zwitterionic or amphoteric surfactant used in composition T can in particular be optionally quaternized aliphatic secondary or tertiary amine derivatives, where the aliphatic group is a straight or branched chain containing 8 to 22 carbon atoms, and the amine derivative contains at least one anionic group, such as a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.

[0064] Preferably, these surfactants are not silicone surfactants.

[0065] Particularly mention may be made of (C8-C 20 ) alkyl betaines, (C8-C 20 ) alkyl sulfobetaines, (C8-C 20 ) alkylamido (C3-C8) alkyl betaines and (C8-C 20 ) alkylamido (C6-C8) alkyl sulfobetaines and mixtures thereof.

[0066] These compounds are classified in the 5th edition (1993) of the CTFA Dictionary under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caproamphodiacetate, disodium caprylamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caproamphodipropionate, disodium caprylamphodipropionate, lauroamphodipropionate and cocoamphodipropionate.

[0067] By way of example, mention may be made of the cocoamphodiacetate sold by Rhodia under the trade name C2M Concentrate.

[0068] Among the compounds which may be used, mention may be made of the compound classified in the CTFA Dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by Chimex under the name Chimexane HB.

[0069] These compounds may be used alone or as mixtures.

[0070] Advantageously, the zwitterionic or amphoteric surfactant is selected from (C8-C 20 ) alkyl betaines, (C8-C 20 ) alkyl sulfobetaines, (C8-C 20 ) alkylamido (C3-C8) alkyl betaines, (C8-C 20 ) alkylamido (C6-C8) alkyl sulfobetaines, and mixtures thereof, more preferably selected from (C8-C 20 ) alkyl betaines, (C8-C 20 ) alkylamido (C3-C8) alkyl betaines and mixtures thereof, and even more preferably selected from (C8-C 20 ) alkylamido (C3-C8) alkyl betaines and mixtures thereof.

[0071] Advantageously, the zwitterionic or amphoteric surfactant is present in a total content ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.75% to 15% by weight, even more preferably from 1% to 10% by weight, and still better from 1.2% to 5% by weight, relative to the total weight of composition T.

[0072] According to a preferred embodiment, composition T comprises one or more anionic surfactants and one or more zwitterionic or amphoteric surfactants.

[0073] Composition T may also contain water, in an amount of at least 60% by weight, still better at least 65% by weight, even still better at least 70% by weight, in particular relative to the total weight of the composition. In particular, the composition may contain water in a total amount ranging from 60% to 98% by weight, preferably from 65% to 95% by weight, more preferably from 70% to 90% by weight, still better from 70% to 85% by weight, relative to the total weight of composition T.

[0074] Additive

[0075] Composition T used in the context of the dyeing method according to the invention may contain any auxiliary agents or additives commonly used.

[0076] Among the additives that may be used, mention may be made of reducing agents, thickeners, softeners, humectants, UV blockers, peptizing agents, solubilizers, fragrances, proteins, vitamins, especially polymers other than silicones, preservatives, oils, waxes and mixtures thereof.

[0077] Polycarbodiimide compound

[0078] Composition C used in the context of the method according to the invention comprises at least one (poly)carbodiimide compound selected from the compounds of formula (II) below.

[0079] The composition may comprise at least two different (poly)carbodiimide compounds, present in the composition as a mixture.

[0080] As shown above, the (poly)carbodiimide compound is selected from the compounds of formula (II) below:

[0081]

[0082] Wherein:

[0083] - X1 and X2 independently represent an oxygen atom O, a sulfur atom S or an NH group;

[0084] -R1 and R2 independently represent hydrocarbon-based groups optionally interrupted by one or more heteroatoms;

[0085] -n and z denote integers ranging from 1 to 20, where n + z ≥ 2 and w denotes an integer ranging from 1 to 3;

[0086] -L1 independently represents a C1-C 18 divalent aliphatic hydrocarbon-based group, a C3-C 15 cycloalkylidene, a C3-C 12 heterocycloalkylidene or a C6-C 14 arylene, and mixtures thereof;

[0087] -E independently represents a group selected from:

[0088] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0089] wherein R3 and R4 independently represent divalent hydrocarbon-based groups optionally interrupted by one or more heteroatoms;

[0090] -R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms;

[0091] -R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

[0092] This specific (poly)carbodiimide compound selected from compounds of formula (II) used in the context of the process according to the invention enables an improvement in the persistence relative to shampooing, for example compared to some other (poly)carbodiimide compounds (especially the compound sold under the name Permutex XR).

[0093] The term "hydrocarbon-based group" means a saturated or unsaturated, straight-chain or branched-chain group containing from 1 to 300 carbon atoms, preferably from 1 to 250 carbon atoms, more preferably from 1 to 200 carbon atoms. Preferably, the hydrocarbon-based group is a saturated straight-chain group.

[0094] The hydrocarbon-based group may contain one or more cyclic groups.

[0095] The hydrocarbon-based group may be interrupted by one or more heteroatoms, especially selected from O, S or N, and / or substituted by one or more cations, anions or zwitterions or cationic groups such as ammonium, anionic groups such as carboxylate, or zwitterionic groups, and / or contain metal ions which can be introduced in the form of salts.

[0096] The term "heteroatom" means an oxygen O, sulfur S or nitrogen N atom, and also a halogen atom, such as Cl, F, Br and I. If a heteroatom is included in the chain of a hydrocarbon-based group, the heteroatom is preferably selected from an oxygen O, sulfur S or nitrogen N atom.

[0097] Preferably, X1 and X2 independently represent an oxygen atom.

[0098] Preferably, R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids and monoalkyl ethers of (poly)alkylene glycols in which the hydroxy group has been removed, and mixtures thereof.

[0099] In a preferred embodiment, R1 and R2 independently are selected from the following groups (i) to (iv):

[0100] (i) A compound of the following formula (III):

[0101] R7-O-C(O)-C(R8)(H)-(III),

[0102] wherein R7 represents a C1-C3 alkyl group, and R8 represents a hydrogen atom or a C1-C3 alkyl group; preferably, R7 is methyl, and R8 is a hydrogen atom or methyl.

[0103] (ii) A compound of the following formula (IV):

[0104] R9-[O-CH2-C(H)(R 10 )] p -(IV),

[0105] wherein R9 represents a C1-C4 alkyl group, R 10 represents a hydrogen atom or a C1-C4 alkyl group and p indicates an integer ranging from 1 to 3; preferably, R9 is methyl, ethyl or butyl, R 10 is a hydrogen atom or methyl and p is equal to 1.

[0106] (iii) A compound of the following formula (V):

[0107] (R 11 )2N-CH2-C(H)(R 12 )-(V),

[0108] wherein R 11 represents a C1-C4 alkyl group, and R 12 represents a hydrogen atom or a C1-C4 alkyl group; preferably, R 11 is methyl, ethyl or butyl, and R 12 is a hydrogen atom or methyl.

[0109] (iv) A compound of the following formula (VI):

[0110] R13 -[O-CH2-C(H)(R 14 )] q -(VI),

[0111] wherein R 13 represents a C1-C4 alkyl or phenyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group and q indicates an integer ranging from 4 to 30; preferably, R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl.

[0112] Preferably, R1 and R2 independently represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0113] According to an alternative embodiment, R1 and R2 are different, and one of the groups R1 or R2 represents a compound of formula (IV) as described above, and the other of the groups R1 or R2 represents a compound of formula (VI) as described above.

[0114] Preferably, in formula (IV), R9 is methyl, ethyl or butyl, and R 10 is a hydrogen atom or methyl and p equals 1.

[0115] Preferably, in formula (VI), R 13 is methyl, ethyl or butyl, and R 14 is a hydrogen atom or methyl and q indicates an integer ranging from 4 to 30.

[0116] According to another alternative embodiment, R1 and R2 are the same and represent a compound of formula (VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably methyl, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30.

[0117] Preferably, n indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0118] Preferably, z indicates an integer ranging from 1 to 20, more preferably from 2 to 20.

[0119] Preferably, w equals 1.

[0120] Preferably, w equals 1, and n + z indicates an integer ranging from 4 to 10.

[0121] Preferably, L1 is selected from C1-C 18 a divalent aliphatic hydrocarbon-based group such as methylene, ethylene and propylene, C3-C 15 a cycloalkylene group such as cyclopentylene, cycloheptylene and cyclohexylene, C3-C 12 a hetero cycloalkylene group such as imidazolylene, pyrrolylene and furanylene, or C6-C 14 an arylene group such as phenylene, and mixtures thereof.

[0122] For example, L1 may be selected from groups derived from the following: toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, norbornane diisocyanate, 2,4-bis(8-isocyanatooctyl)-1,3-dioctylcyclobutane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate and phenylene diisocyanate, and mixtures thereof.

[0123] Preferably, L1 is selected from C3-C 15 a cycloalkylene group or C6-C 14 an arylene group, and mixtures thereof, such as a compound of the following formula (VII):

[0124]

[0125] Preferably, L1 is 4,4-dicyclohexylenemethane corresponding to the following formula (VIII):

[0126]

[0127] According to another embodiment, when L1 is a C6-C 14 arylene group, L1 is not m-tetramethylxylylene represented by the following formula (IX):

[0128]

[0129] As previously indicated, E independently represents a group selected from the following:

[0130] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0131] wherein R3 and R4 independently represent a divalent hydrocarbon-based group optionally inserted with one or more heteroatoms;

[0132] - R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally inserted with one or more heteroatoms; and

[0133] - R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally inserted with one or more heteroatoms.

[0134] Preferably, R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 cycloalkylene groups such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0135] More preferably, R3 and R4 are independently selected from straight-chain or branched C1-C optionally inserted with one or more heteroatoms 18 alkylene groups, such as methylene, butylene, propylene or ethylene.

[0136] Preferably, when R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 cycloalkylene groups such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0137] Preferably, R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene groups such as phenylene, C3-C 12 cycloalkylene groups such as cyclopropylene and cyclobutylene, straight-chain or branched C1-C 18 alkylene groups such as methylene and ethylene, and mixtures thereof.

[0138] Preferably, E represents the group -O-R3-O-, wherein R3 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene groups, C3-C 12 cycloalkylene groups, straight-chain or branched C1-C 18 alkylene groups, and mixtures thereof.

[0139] More preferably, E represents the group -O-R3-O-, wherein R3 represents a straight-chain or branched C1-C optionally inserted with one or more heteroatoms 18 alkylene group, such as methylene, butylene, propylene or ethylene.

[0140] According to a specific embodiment, the (poly)carbodiimide compound is a copolymer derived from α-methylstyryl isocyanate of the following formula (X):

[0141]

[0142] wherein R independently represents an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, or an aryl group having 6 to 24 carbon atoms, and

[0143] n indicates an integer ranging from 2 to 100.

[0144] In this embodiment, the term "alkyl group" is as defined previously.

[0145] In this embodiment, the term "cycloalkyl group" is as defined previously.

[0146] In this embodiment, n may indicate an integer ranging from 2 to 50, preferably from 3 to 30, and even more preferably from 5 to 10.

[0147] According to another specific embodiment, the (poly)carbodiimide compound is a compound of the following formula (XI):

[0148]

[0149] wherein R independently represents an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, or an aryl group having 6 to 24 carbon atoms.

[0150] "Alkyl group", "cycloalkyl group" and "aryl group" are as defined previously.

[0151] According to a preferred embodiment, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0152] - X1 and X2 independently represent an oxygen atom;

[0153] - R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof, preferably monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, more preferably the compound of formula (VI) described previously, wherein R 13 represents a C1-C4 alkyl group or a phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0154] - n and z (when they are present) indicate integers ranging from 1 to 20, wherein n + z ≥ 2 and w is equal to 1;

[0155] - L1 (when it is present) is selected from C1-C 18A divalent aliphatic hydrocarbon-based group, C3-C 15 cycloalkylene, C3-C 12 heterocycloalkylene or C6-C 14 arylene, and mixtures thereof, preferably C3-C 15 cycloalkylene;

[0156] -A (when present) is selected from C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 cycloalkylene, C3-C 12 heterocycloalkylene or C6-C 14 arylene, and mixtures thereof, preferably C3-C 15 cycloalkylene;

[0157] -E (when present) independently represents a group selected from:

[0158] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0159] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0160] -When R5 is not a covalent bond, R5 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and

[0161] -R6 (when present) is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0162] Preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0163] -X1 and X2 independently represent an oxygen atom;

[0164] -R1 and R2 are independently selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols from which the hydroxy group has been removed, and mixtures thereof;

[0165] -n and z denote integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0166] -L1 is selected from C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylene group, C3-C 12 a heteroalkylene group or C6-C 14 an arylene group, and mixtures thereof;

[0167] -E independently represents a group selected from:

[0168] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0169] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 an arylene group, C3-C 12 a cycloalkylene group, linear or branched C1-C 18 an alkylene group, and mixtures thereof;

[0170] -When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 an arylene group, C3-C 12 a cycloalkylene group, linear or branched C1-C 18 an alkylene group, and mixtures thereof; and

[0171] -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 an arylene group, C3-C 12 a cycloalkylene group, linear or branched C1-C 18 an alkylene group, and mixtures thereof.

[0172] More preferably, the (poly)carbodiimide compound is selected from the compounds of formula (II), wherein:

[0173] -X1 and X2 independently represent an oxygen atom;

[0174] -R1 and R2 are independently a monoalkyl ether of a (poly)alkylene glycol from which the hydroxyl group has been removed;

[0175] -n and z denote integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1;

[0176] -L1 is C3-C 15 a cycloalkylene group;

[0177] -E independently represents a group selected from:

[0178] -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-;

[0179] wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof;

[0180] - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and

[0181] - R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

[0182] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0183] - X1 and X2 independently represent an oxygen atom;

[0184] - R1 and R2 independently represent the following compound of formula (VI):

[0185] R 13 -[O-CH2-C(H)(R 14 )] q - (VI),

[0186] wherein R 13 represents C1-C4 alkyl or phenyl, preferably C1-C4 alkyl, more preferably methyl, R 14 represents a hydrogen atom or C1-C4 alkyl, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0187] - n and z indicate integers ranging from 1 to 20, wherein n + z ranges from 4 to 10 and w is equal to 1;

[0188] - L1 is C3-C 15 cycloalkylene, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and

[0189] - E represents the group -O-R3-O-, wherein R3 is selected from C6-C optionally inserted with one or more heteroatoms14 Arylene, C3-C 12 Cycloalkylene, linear or branched C1-C 18 Alkylene, and mixtures thereof.

[0190] Even more preferably, the (poly)carbodiimide compound is selected from compounds of formula (II), wherein:

[0191] -X1 and X2 independently represent an oxygen atom;

[0192] -R1 and R2 independently represent a compound of the following formula (VI):

[0193] R 13 -[O-CH2-C(H)(R 14 )] q -(VI)

[0194] wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30;

[0195] -n and z indicate integers ranging from 1 to 20, wherein n + z ranges from 4 to 10 and w is equal to 1;

[0196] -L1 is a C3-C 15 cycloalkylene group, such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and

[0197] -E represents the group -O-R3-O-, wherein R3 represents a linear or branched C1-C 18 alkylene group optionally inserted with one or more heteroatoms, such as methylene, propylene, butylene or ethylene.

[0198] According to a preferred embodiment, the (poly)carbodiimide compound is a compound of the following formula (XII):

[0199]

[0200] wherein L1 is 4,4-dicyclohexylmethane, n and z indicate integers ranging from 1 to 20, wherein n + z ranges from 4 to 10, E represents the group -O-R3-O-, wherein R3 represents a linear or branched C1-C 18 alkylene group optionally inserted with one or more heteroatoms, such as methylene, propylene, butylene or ethylene, and r and s indicate integers ranging from 4 to 30.

[0201] Advantageously, the total amount of the (poly)carbodiimide compound ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight and still better from 1% to 6% by weight, relative to the total weight of composition C.

[0202] Colorant

[0203] Composition C used in the context of the method according to the invention comprises one or more colorants selected from pigments, direct dyes and mixtures thereof.

[0204] Preferably, composition C used in the context of the method according to the invention comprises one or more pigments.

[0205] The term "pigment" refers to any pigment that imparts color to the keratin material. They have a solubility in water at 25 °C and atmospheric pressure (760 mmHg) of less than 0.05% by weight and preferably less than 0.01% by weight.

[0206] Pigments that can be used are especially selected from organic and / or mineral pigments known in the art, especially those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and Ullmann’s Encyclopedia of Industrial Chemistry.

[0207] They can be natural, of natural origin or non-natural.

[0208] These pigments can be in the form of pigment powders or pastes. They can be coated or uncoated.

[0209] Pigments can be selected, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as mother-of-pearl or glitter flakes, and mixtures thereof.

[0210] Pigments can be mineral pigments. The term "mineral pigment" refers to any pigment that meets the definition in the chapter on inorganic pigments in Ullmann’s encyclopedia. Among the mineral pigments available in the present invention, iron oxide, chromium oxide, manganese violet, ultramarine, chromium hydrate, iron blue and titanium oxide can be mentioned.

[0211] Pigments can be organic pigments. The term "organic pigment" refers to any pigment that meets the definition in the chapter on organic pigments in Ullmann’s Encyclopedia.

[0212] The organic pigments may in particular be selected from nitroso, nitro, azo, xanthene, pyrene, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

[0213] In particular, the white or coloured organic pigments may be selected from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, blue pigments numbered in the Color Index with index numbers CI 42090, 69800, 69825, 74100, 74160, yellow pigments numbered in the Color Index with index numbers CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments numbered in the Color Index with index numbers CI 61565, 61570, 74260, orange pigments numbered in the Color Index with index numbers CI 11725, 45370, 71105, red pigments numbered in the Color Index with index numbers CI12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, such as the pigments obtained by oxidative polymerization of indole or phenol derivatives as described in patent FR 2 679 771.

[0214] Examples which may also be mentioned include pigment pastes of organic pigments, such as the products sold by Hoechst under the following names:

[0215] -Cosmenyl Yellow 10G: Pigment Yellow 3 (CI 11710);

[0216] -Cosmenyl Yellow G: Pigment Yellow 1 (CI 11680);

[0217] -Cosmenyl Orange GR: Pigment Orange 43 (CI 71105);

[0218] -Cosmenyl Red R: Pigment Red 4 (CI 12085);

[0219] -Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);

[0220] - Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);

[0221] - Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160);

[0222] - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

[0223] - Cosmenyl Black R: Pigment Black 7 (CI 77266).

[0224] The pigments according to the invention can also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments can in particular consist of particles which include an inorganic core, at least one binder for attaching the organic pigment to the core, and at least one organic pigment which at least partly covers the core.

[0225] The organic pigment can also be a lake. The term "lake" refers to a dye adsorbed on an insoluble particle, and the assembly thus obtained remains insoluble during use.

[0226] Inorganic substrates on which the dye is adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium.

[0227] Among these dyes, carminic acid can be mentioned. Dyes known under the following names can also be mentioned: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI15 985), D&C Green (CI 61 570), D&C Yellow 10 (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42090).

[0228] Examples of lakes that can be mentioned are products known under the following names: D&C Red 7 (CI 15 850:1).

[0229] The pigment can also be a pigment with special effects. The term "pigment with special effects" means a pigment that generally produces a non-uniform colored appearance (characterized by a certain chroma, a certain vivacity, and a certain brightness level) that varies with the observation conditions (light, temperature, viewing angle, etc.). Thus, they are different from colored pigments that provide standard uniform opaque, translucent, or transparent hues.

[0230] There are several types of pigments with special effects: those with a low refractive index, such as fluorescent or photochromic pigments, and those with a higher refractive index, such as nacre, interference pigments, or glitter flakes.

[0231] Examples of pigments with special effects that can be mentioned include pearlescent pigments, such as mica coated with titanium or coated with bismuth oxychloride; colored pearlescent pigments, such as mica coated with titanium and iron oxides, mica coated with iron oxides, mica coated with titanium and especially coated with iron blue or coated with chromium oxides, mica coated with titanium and organic pigments as previously defined, and also pearlescent pigments based on bismuth oxychloride. Mentionable pearlescent pigments include nacre Cellini (mica - TiO2 - lake) sold by BASF, Prestige (mica - TiO2) sold by Eckart, Prestige Bronze (mica - Fe2O3) sold by Eckart, and Colorona (mica - TiO2 - Fe2O3) sold by Merck.

[0232] It is also possible to mention nacre, in particular sold by BASF under the names Brilliant Gold 212G (Timica), Gold 222C (Cloisonne), Sparkle Gold (Timica), Gold 4504 (Chromalite) and Monarch Gold 233X (Cloisonne); bronze nacre, in particular sold by Merck under the names Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by BASF under the name Super Bronze (Cloisonne); orange nacre, in particular sold by BASF under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by Merck under the names Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown nacre, in particular sold by BASF under the names Nu-antique Copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacre with a copper-colored tone, in particular sold by BASF under the name Copper 340A (Timica); nacre with a red tone, in particular sold by Merck under the name Sienna Fine (17386) (Colorona); nacre with a yellow tone, in particular sold by BASF under the name Yellow (4502) (Chromalite); red nacre with a golden tone, in particular sold by BASF under the name Sunstone G012 (Gemtone); pink nacre, in particular sold by BASF under the name Tan Opale G005 (Gemtone); black nacre with a golden tone, in particular sold by BASF under the name Nu-antique Bronze 240AB (Timica); blue nacre, in particular sold by Merck under the name Matte Blue (17433) (Microna); white nacre with a silver tone, in particular sold by Merck under the name Xirona Silver; and golden-green pink-orange nacre, in particular sold by Merck under the name Indian Summer (Xirona); and mixtures thereof.

[0233] Still as an example of nacre, it is also possible to mention particles comprising a borosilicate substrate coated with titanium oxide.

[0234] Particles comprising a glass substrate coated with titanium oxide are in particular sold by Toyal under the name Metashine MC1080RY.

[0235] Finally, examples of nacre that can also be mentioned include polyethylene terephthalate glitter flakes, in particular those sold by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver glitter flakes). Multilayer pigments based on synthetic substrates can also be envisaged, such as alumina, silica, calcium sodium borosilicate, calcium aluminium borosilicate and aluminium.

[0236] Pigments with special effects can also be selected from reflective particles, i.e. in particular from particles whose size, structure, in particular the thickness of the layer they form, and their physical and chemical properties as well as surface state allow them to reflect incident light. If appropriate, when applied to the carrier to be made up, this reflection can have an intensity sufficient to produce high - light points visible to the naked eye on the surface of the composition or mixture, i.e. points that make them appear to sparkle and are brighter in contrast to their surroundings.

[0237] Reflective particles can be chosen so as not to significantly alter the coloring effect produced by the colorants combined with them, and more particularly so as to optimize this effect in terms of color reproduction. They can more particularly have a yellow, pink, red, bronze, orange, brown, gold and / or copper color or hue.

[0238] These particles can have different forms and can in particular be in the form of flakes or spheres, especially in the form of spheres.

[0239] Regardless of their form, reflective particles can have or can not have a multilayer structure, and in the case of a multilayer structure, can have for example at least one layer of uniform thickness, especially of a reflective material.

[0240] When the reflective particles do not have a multilayer structure, they can be composed of, for example, metal oxides, especially titanium or iron oxides obtained synthetically.

[0241] When the reflective particles have a multilayer structure, they can include for example a natural or synthetic substrate, especially a synthetic substrate at least partially coated with at least one layer of a reflective material, especially at least one metal or metallic material. The substrate can be made of one or more organic and / or mineral materials.

[0242] More particularly, it can be selected from glass, ceramics, graphite, metal oxides, alumina, silica, silicates (especially aluminosilicates and borosilicates), and synthetic mica, and mixtures thereof, this list not being restrictive.

[0243] The reflective material may include a metal layer or a layer of a metallic material.

[0244] Reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

[0245] In addition, as an example of reflective particles comprising a mineral substrate coated with a metal layer, mention may also be made of particles comprising a silver-coated borosilicate substrate.

[0246] Particles having a silver-coated glass substrate in flake form are sold by Toyo Corporation under the name Microglass Metashine REFSX 2025PS. Particles having a glass substrate coated with a nickel / chromium / molybdenum alloy are sold by the same company under the names Crystal Star GF 550 and GF 2525.

[0247] Particles comprising a metallic substrate may also be used, said metallic substrate such as silver, aluminium, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze or titanium, said substrate being coated with at least one layer of at least one metal oxide, said at least one metal oxide such as titanium oxide, aluminium oxide, iron oxide, cerium oxide, chromium oxide, silicon oxide, and mixtures thereof.

[0248] Examples that may be mentioned include aluminium powder, bronze powder or copper powder coated with SiO2, which are sold by Eckart under the name Visionaire.

[0249] Interference pigments not attached to a substrate may also be mentioned, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectraf / x from Spectratek). Special effect pigments also include fluorescent pigments (whether these are substances that fluoresce in daylight or produce UV fluorescence), phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example sold by Quantum Dots Corporation.

[0250] The various pigments that can be used in the compositions according to the invention make it possible to obtain a wide range of colours, as well as specific optical effects, such as metallic effects or interference effects.

[0251] The size of the pigments used in the compositions according to the invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm and more preferably between 30 nm and 50 μm.

[0252] The pigment may be dispersed in the composition by a dispersant.

[0253] Dispersants are used to protect the dispersed particles from agglomeration or flocculation. The dispersants can be surfactants, oligomers, polymers or mixtures of several thereof carrying one or more functional groups with a strong affinity for the surface of the particles to be dispersed. In particular, they can become physically or chemically attached to the surface of the pigment. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. In particular, use is made of esters of, in particular, 12-hydroxystearic acid and of C8 to C20 fatty acids and of polyols such as glycerol or diglycerol, for example poly(12-hydroxystearic acid)stearate having a molecular weight of about 750 g / mol, such as the product sold under the name Solsperse 21 000 by Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by Henkel, or polyhydroxystearic acids such as the product sold under the reference Arlacel P100 by Uniqema, and mixtures thereof.

[0254] As other dispersants that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, such as Solsperse 17 000 sold by Avicia, and polydimethylsiloxane / propylene oxide mixtures, such as those sold under the references DC2-5185 and DC2-5225 C by Dow Corning.

[0255] The pigments used in the composition may be surface treated with an organic agent.

[0256] Thus, pigments that have been pre-surface-treated and are available in the context of the present invention are pigments that have been subjected in whole or in part to a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature with an organic reagent and are then dispersed in the composition according to the present invention, such organic reagents being in particular those described in Cosmetics and Toiletries, February 1990, Vol. 105, pp. 53-64. These organic reagents can for example be selected from waxes such as carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and their derivatives; anionic surfactants; lecithin; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids such as aluminium stearate or aluminium laurate; metal alkoxides; polyethylene; (meth)acrylic polymers such as polymethyl methacrylate; polymers and copolymers containing acrylate units; alkanolamines; silicone compounds such as silicones, in particular polydimethylsiloxane; organic fluorine compounds such as perfluoroalkyl ethers; fluorosilicone compounds.

[0257] The surface-treated pigments that can be used in the composition can also have been treated with a mixture of these compounds and / or may have undergone several surface treatments.

[0258] The surface-treated pigments that can be used in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or can be commercially available as such.

[0259] Preferably, the surface-treated pigments are coated with an organic layer.

[0260] The organic reagent for treating the pigments can be attached to the pigments by evaporation of the solvent, by chemical reaction between the molecules of the surfactant or by formation of a covalent bond between the surfactant and the pigment.

[0261] The surface treatment can thus be carried out for example by a chemical reaction of the surfactant with the pigment surface and by formation of a covalent bond between the surfactant and the pigment or filler. This method is in particular described in patent US 4 578 266.

[0262] Preferably, an organic reagent that is covalently bonded to the pigment is used.

[0263] The reagent for surface treatment can be present in an amount by weight from 0.1% to 50%, preferably by weight from 0.5% to 30% and even more preferably by weight from 1% to 20% relative to the total weight of the surface-treated pigment.

[0264] Preferably, the surface treatment agent for the pigments is selected from the following treatment agents:

[0265] - PEG - silicone treating agents, such as the AQ surface treating agent sold by LCW;

[0266] - Polymethylsiloxane treating agents, such as the SI surface treating agent sold by LCW;

[0267] - Polydimethylsiloxane treating agents, such as the Covasil 3.05 surface treating agent sold by LCW;

[0268] - Polydimethylsiloxane / trimethylsilyl silicate treating agents, such as the Covasil 4.05 surface treating agent sold by LCW;

[0269] - Magnesium myristate treating agents, such as the MM surface treating agent sold by LCW;

[0270] - Aluminum dimyristate treating agents, such as the MI surface treating agent sold by Miyoshi;

[0271] - Perfluoropoly(methyl isopropyl ether) treating agents, such as the FHC surface treating agent sold by LCW;

[0272] - Isostearyl sebacate treating agents, such as the HS surface treating agent sold by Miyoshi;

[0273] - Perfluoroalkyl phosphate treating agents, such as the PF surface treating agent sold by Daito;

[0274] - Acrylate / polydimethylsiloxane copolymer and perfluoroalkyl phosphate treating agents, such as the FSA surface treating agent sold by Daito;

[0275] - Polymethylhydrosiloxane / perfluoroalkyl phosphate treating agents, such as the FS01 surface treating agent sold by Daito;

[0276] - Acrylate copolymer / polydimethylsiloxane treating agents, such as the ASC surface treating agent sold by Daito;

[0277] - Isopropyl triisostearoyl titanate treating agents, such as the ITT surface treating agent sold by Daito;

[0278] - Acrylate copolymer treating agents, such as the APD surface treating agent sold by Daito;

[0279] - Perfluoroalkyl phosphate / isopropyl triisostearoyl titanate treating agents, such as the PF + ITT surface treating agent sold by Daito.

[0280] According to specific embodiments of the present invention, the dispersant is present together with organic or mineral pigments in the form of sub - micron - sized particles.

[0281] The term "submicron-sized" or "submicron" means that the pigment has a particle size that has been micronized by a micronization method and has an average particle size of less than one micron (μm), in particular between 0.1 and 0.9 μm and preferably between 0.2 and 0.6 μm.

[0282] According to one embodiment, the dispersant and the pigment are present in an amount (dispersant:pigment) according to a weight ratio between 1:4 and 4:1, in particular between 1.5:3.5 and 3.5:1 or even better between 1.75:3 and 3:1.

[0283] Thus, the dispersant can have a silicone backbone, such as silicone polyethers and dispersants of the aminosilicone type other than the aminosilicones mentioned below. Among suitable dispersants, mention may be made of:

[0284] - Aminosilicones, i.e. silicones containing one or more amine groups, such as those sold under the following names and index numbers: BYK LPX 21879 from BYK Chemie GmbH, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 and GP-988-1 sold by Genesee Polymers,

[0285] - Silicone acrylates, such as those sold by Evonik RC 902, RC 922, RC 1041 and RC 1043,

[0286] - Carboxyl-carrying polydimethylsiloxane (PDMS) silicones such as X-22162 and X-22370 from Shin-Etsu Chemical Co., Ltd., epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682 and GP-695 from Genesee Polymers, or RC 1401, RC 1403, RC 1412.

[0287] According to a specific embodiment, the dispersant is of the aminosilicone type other than the aminosilicones mentioned below and is cationic.

[0288] Preferably, the pigment is selected from mineral pigments, mixed mineral-organic pigments or organic pigments.

[0289] In a variant of the present invention, the pigment is an organic pigment, preferably an organic pigment surface-treated with an organic reagent selected from silicone compounds. In another variant of the present invention, the pigment is a mineral pigment.

[0290] Preferably, the pigment is selected from iron oxides, especially red, brown or black iron oxides. As an example of iron oxide, mention may be made of the iron oxide sold by Sun Chemical under the name Red Iron Oxide.

[0291] Direct dyes

[0292] The composition C used in the context of the method according to the invention may comprise one or more direct dyes.

[0293] The term "direct dyes" means natural and / or synthetic dyes, other than oxidation dyes. These are dyes that will spread superficially on the fiber.

[0294] They can be ionic or non-ionic, preferably cationic or non-ionic.

[0295] Examples of suitable direct dyes that may be mentioned include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryl types; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of a mixture.

[0296] The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazinium cationic dyes of the following formulas (XIII) and (XIV) and the azo cationic dyes of the formulas (XV) and (XVI):

[0297] Het + -N(Ra)-N=C(Rb)-Ar,Q-(XIII),

[0298] Het + -C(Ra)=N-N(Rb)-Ar,Q(XIV),

[0299] Het + -N=N-Ar,Q-(XV),

[0300] Ar + -N=N=Ar”,Q-(XVI),

[0301] In the formulas (XIII) to (XVI):

[0302] -Het +represents a cationic heteroaryl preferably carrying a cationic charge within the ring, such as imidazolium, indolium or pyridinium, which is optionally preferably substituted by at least one (C1-C8) alkyl group such as methyl;

[0303] -Ar + represents an aryl carrying a cationic charge outside the ring, preferably ammonium, especially tri(C1-C8)alkylammonium such as trimethylammonium, such as phenyl or naphthyl;

[0304] -Ar represents an aryl, especially phenyl, which is optionally preferably substituted by one or more electron-donating groups, such as i) an optionally substituted (C1-C8) alkyl group, ii) an optionally substituted (C1-C8) alkoxy group, iii) a (di)(C1-C8)(alkyl)amino group optionally substituted by a hydroxyl group on the alkyl, iv) an aryl(C1-C8)alkylamino group, v) an optionally substituted N-(C1-C8)alkyl-N-aryl(C1-C8)alkylamino group, or alternatively, Ar represents a julolidine group;

[0305] -Ar” represents an optionally substituted (hetero)aryl, such as phenyl or pyrazolyl, which is optionally preferably substituted by one or more (C1-C8) alkyl groups, hydroxyl groups, (di)(C1-C8)(alkyl)amino groups, (C1-C8) alkoxy groups or phenyl groups;

[0306] -Ra and Rb may be the same or different and represent a hydrogen atom or an optionally preferably hydroxyl-substituted (C1-C8) alkyl group;

[0307] or alternatively, the substituent Ra and Het + and / or the substituent of Rb and Ar together with the atoms carrying them form a (hetero)cycloalkyl group; in particular, Ra and Rb represent a hydrogen atom or a (C1-C4) alkyl group optionally substituted by a hydroxyl group;

[0308] -Q- represents an organic or inorganic anion counterion, such as a halide ion or an alkyl sulfate.

[0309] In particular, mention may be made of azo and hydrazo direct dyes carrying a cationic charge within the ring, such as those of formulae (XIII) to (XVI) as previously defined, and more particularly the cationic direct dyes carrying a cationic charge within the ring described in patent applications WO 95 / 15144, WO 95 / 01772 and EP 714 954, preferably the following direct dyes:

[0310]

[0311] In formulae (XVII) and (XVIII):

[0312] -R 1represents a (C1-C4) alkyl group such as methyl;

[0313] -R 2 and R 3 may be the same or different and represents a hydrogen atom or a (C1-C4) alkyl group such as methyl; and

[0314] -R 4 represents a hydrogen atom or an electron-donating group such as an optionally substituted (C1-C8) alkyl group, an optionally substituted (C1-C8) alkoxy group, or a (di)(C1-C8)(alkyl)amino group optionally substituted by a hydroxyl group on the alkyl; in particular, R 4 is a hydrogen atom;

[0315] -Z represents a CH group or a nitrogen atom, preferably CH;

[0316] -Q- is an anion counterion as previously defined, particularly a halide ion such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

[0317] In particular, the dyes of formula (XV) and (XVI) are selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives, where Q’ is an anion counterion as previously defined, particularly a halide ion such as chloride, or an alkyl sulfate such as methyl sulfate or mesyl.

[0318] The direct dyes can be selected from anionic direct dyes. The anionic direct dyes of the present invention are dyes that are usually referred to as "acid" direct dyes due to their affinity for basic substances. The term "anionic direct dye" means any direct dye that includes at least one CO2R or SO3R substituent in its structure, where R indicates a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. The anionic dyes can be selected from direct nitro acid dyes, azo acid dyes, azine acid dyes, triarylmethane acid dyes, indoamine acid dyes, anthraquinone acid dyes, indigo dyes and natural acid dyes.

[0319] As acid dyes that can be used in the present invention, the following dyes of formula (XIX), (XIX’), (XX), (XX’), (XXI), (XXI’), (XXII), (XXII’), (XXIII), (XXIV), (XXV) and (XXVI) can be mentioned:

[0320] a) Diaryl anionic azo dyes of formula (XIX) or (XIX’):

[0321]

[0322] In formulas (XIX) and (XIX’):

[0323] -R7, R8, R9, R 10 , R’7, R’8, R’9 and R’ 10 may be the same or different and represent a hydrogen atom or a group selected from the following:

[0324] - alkyl;

[0325] - alkoxy, alkylthio;

[0326] - hydroxy, mercapto;

[0327] - nitro, nitroso;

[0328] - R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X”, where R° represents a hydrogen atom or an alkyl or aryl group; X, X’ and X” may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0329] -(O)2S(O - ), -M + , where M + represents a hydrogen atom or a cationic counterion;

[0330] -(O)CO - , -M + , where M + is as previously defined;

[0331] - R”-S(O)2-, where R” represents a hydrogen atom or an alkyl, aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferably phenylamino or phenyl;

[0332] - R”’-S(O)2-X’-, where R”’ represents an optionally substituted alkyl or aryl group and X’ is as previously defined;

[0333] -(di)(alkyl)amino;

[0334] - aryl(alkyl)amino, optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii)(O)2S(O - ), -M + and iv) alkoxy, where M + is as previously defined;

[0335] - optionally substituted heteroaryl; preferably benzothiazolyl;

[0336] - cycloalkyl, especially cyclohexyl;

[0337] - Ar-N=N-, where Ar represents an optionally substituted aryl group; preferably optionally substituted by one or more alkyl, (O)2S(O -)-,M + or a phenyl group substituted with a phenylamino group;

[0338] - or alternatively, two adjacent groups R7 and R8, or R8 and R9, or R9 and R 10 together form a fused benzo group A'; and R'7 and R'8, or R'8 and R'9, or R'9 and R' 10 together form a fused benzo group B'; wherein A' and B' are optionally substituted with one or more groups selected from the following: i) nitro; ii) nitroso; iii) (O)2S(O - )-,M + ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; x) Ar-N=N- and xi) optionally substituted aryl(alkyl)amino; wherein M + , R°, X, X', X'' and Ar are as defined previously;

[0339] -W represents a sigma bond σ, an oxygen or sulfur atom, or a divalent group i) -NR-, where R is as defined previously, or ii) methylene -C(Ra)(Rb)-, where Ra and Rb may be the same or different and represent a hydrogen atom or an aryl group, or alternatively, Ra and Rb together with the carbon atom carrying them form a spiroalkyl group; preferably, W represents a sulfur atom or Ra and Rb together form a cyclohexyl group;

[0340] It should be understood that formula (XIX) and (XIX') contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group (O)CO - -,M + ; preferably sodium sulfonate.

[0341] As examples of the dyes of formula (XIX), mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3, Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or Sunset Yellow;

[0342] And, as examples of the dyes of formula (XIX'), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38;

[0343] b) Pyrazolone anion azo dyes of formula (XX) and (XX'):

[0344]

[0345] In formulae (XX) and (XX'):

[0346] -R 11 、R 12 and R 13 may be the same or different and represent a hydrogen or halogen atom, an alkyl group or -(O)2S(O - ),M + where M + is as previously defined;

[0347] -R 14 represents a hydrogen atom, an alkyl group or the group -C(O)O - ,M + where M + is as previously defined;

[0348] -R 15 represents a hydrogen atom;

[0349] -R 16 represents an oxo group, in which case R' 16 is absent, or alternatively, R 15 and R 16 together form a double bond;

[0350] -R 17 and R 18 may be the same or different and represent a hydrogen atom or a group selected from:

[0351] -(O)2S(O - )-,M + , where M + is as previously defined;

[0352] -Ar-O-S(O)2-, where Ar represents an optionally substituted aryl group; preferably a phenyl group optionally substituted by one or more alkyl groups;

[0353] -R 19 and R 20 together form a double bond, or an optionally substituted benzoyl group D';

[0354] -R' 16 , R' 19 and R' 20 may be the same or different and represent a hydrogen atom, an alkyl group or a hydroxyl group;

[0355] -R 21 represents a hydrogen atom, an alkyl group or an alkoxy group;

[0356] -Ra and Rb may be the same or different, as previously defined; preferably, Ra represents a hydrogen atom and Rb represents an aryl group;

[0357] -Y represents a hydroxyl group or an oxo group;

[0358] - represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

[0359] It should be understood that formula (XX) and (XX') contain at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group -C(O)O - ,M + ; preferably sodium sulfonate.

[0360] As examples of the dyes of formula (XX), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and as examples of the dyes of formula (XX'), mention may be made of: Acid Yellow 17;

[0361] c) Anthraquinone dyes of formula (XXI) and (XXI'):

[0362]

[0363] In formula (XXI) and (XXI'):

[0364] -R 22 , R 23 , R 24, R 25 , R 26 and R 27 may be the same or different and represent a hydrogen or halogen atom, or a group selected from:

[0365] - alkyl;

[0366] - hydroxy, mercapto;

[0367] - alkoxy, alkylthio;

[0368] - optionally substituted aryloxy or arylthio, preferably substituted by one or more groups selected from alkyl and (O)2S(O - ), M + , where M + is as previously defined;

[0369] - aryl(alkyl)amino, optionally substituted by one or more groups selected from alkyl and (O)2S(O - ), M + , where M + is as previously defined;

[0370] - (di)(alkyl)amino;

[0371] - (di)(hydroxyalkyl)amino;

[0372] - (O)2S(O - ), M + , where M + is as previously defined;

[0373] - Z’ represents a hydrogen atom or the group NR 28 R 29 , where R 28 and R 29 may be the same or different and represent a hydrogen atom or a group selected from:

[0374] - alkyl;

[0375] - polyhydroxyalkyl, such as hydroxyethyl;

[0376] - aryl optionally substituted by one or more groups, especially the following: i) alkyl, such as methyl, n - dodecyl, n - butyl; ii)(O)2S(O - ), M + , where M + is as previously defined; iii)R° - C(X)-X’-, R° - X’-C(X)-, R° - X’-C(X)-X”, where R°, X, X’ and X” are as previously defined, preferably R° represents alkyl;

[0377] - cycloalkyl, especially cyclohexyl;

[0378] -Z represents a group selected from hydroxy and NR' 28 R' 29 wherein R' 28 and R' 29 may be the same or different and represent an atom or group as defined previously for R 28 and R 29 ;

[0379] It should be understood that formulae (XXI) and (XXI') contain at least one sulphonate group (O)2S(O - ),M + or a carboxylate group C(O)O - ,M + ; preferably sodium sulphonate.

[0380] As examples of the dyes of formula (XXI), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; EXT Violet No.2; and, as examples of the dyes of formula (XXI'), mention may be made of: Acid Black 48;

[0381] d) Nitro dyes of formulae (XXII) and (XXII'):

[0382]

[0383] In formulae (XXII) and (XXII'):

[0384] -R 30 、R 31 and R 32 may be the same or different and represent a hydrogen atom or a halogen atom or a group selected from:

[0385] -alkyl;

[0386] -alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;

[0387] -hydroxy, mercapto;

[0388] -nitro, nitroso;

[0389] -polyhaloalkyl;

[0390] -R°-C(X)-X'-、R°-X'-C(X)-、R°-X'-C(X)-X", where R°, X, X' and X" are as defined previously;

[0391] -(O)2S(O - )-, M + where M + is as previously defined;

[0392] -(O)CO - -, M + where M + is as previously defined;

[0393] -(di)(alkyl)amino;

[0394] -(di)(hydroxyalkyl)amino;

[0395] -heterocycloalkyl, such as piperidino, piperazino or morpholino; in particular, R 30 , R 31 and R 32 represent a hydrogen atom;

[0396] -Rc and Rd may be the same or different and represent a hydrogen atom or an alkyl group;

[0397] -W is as previously defined; W in particular represents an -NH- group;

[0398] -ALK represents a straight-chain or branched divalent C1-C6 alkylene group; in particular, ALK represents a -CH2-CH2- group;

[0399] -n is 1 or 2;

[0400] -p represents an integer between 1 and 5 inclusive;

[0401] -q represents an integer between 1 and 4 inclusive;

[0402] -u is 0 or 1;

[0403] -when n is 1, J represents a nitro or nitroso group; in particular, nitro;

[0404] -when n is 2, J represents an oxygen or sulfur atom, or a divalent group -S(O)m-, where m represents the integer 1 or 2; preferably, J represents a -SO2- group;

[0405] -M’ represents a hydrogen atom or a cationic counterion;

[0406] - may be present or absent and represents an optionally substituted benzoyl group by one or more groups R 30 as previously defined;

[0407] It should be understood that formulae (XXII) and (XXII’) contain at least one sulfonate group (O)2S(O - )-, M+ or a carboxylate group C(O)O - , M + ; preferably sodium sulfonate.

[0408] As examples of the dyes of formula (XXII), mention may be made of: Acid Brown 13 and Acid Orange 3; as examples of the dyes of formula (XXII’), mention may be made of: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidyl-5-nitrobenzenesulfonic acid, 2-(4’-N,N-(2”-hydroxyethyl)amino-2’-nitro)anilinoethanesulfonic acid, the sodium salt of 4-β-hydroxyethylamino-3-nitrobenzenesulfonic acid; External D&C Yellow 7 (EXT D&C Yellow 7);

[0409] e) Triarylmethane dyes of formula (XXIII):

[0410]

[0411] In formula (XXIII):

[0412] -R 33 , R 34 , R 35 and R 36 may be the same or different and represent a hydrogen atom or a group selected from: alkyl, optionally substituted aryl and optionally substituted aralkyl; in particular alkyl and optionally the group (O) m S(O - )-, M + substituted benzyl, where M + and m are as defined previously;

[0413] -R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 may be the same or different and represent a hydrogen atom or a group selected from:

[0414] - alkyl;

[0415] - alkoxy, alkylthio;

[0416] - (di)(alkyl)amino;

[0417] - hydroxy, mercapto;

[0418] - nitro, nitroso;

[0419] -R°-C(X)-X’-, R°-X’-C(X)-, R°-X’-C(X)-X’’, where R° represents a hydrogen atom, an alkyl group or an aryl group; X, X’ and X’’ may be the same or different and represent an oxygen or sulfur atom, or NR, where R represents a hydrogen atom or an alkyl group;

[0420] -(O)2S(O - )-, M + , where M + represents a hydrogen atom or a cationic counterion;

[0421] -(O)CO - -, M + , where M + is as previously defined;

[0422] -Or alternatively, two adjacent groups R 41 and R 42 or R 42 and R 43 or R 43 and R 44 together form a fused benzo group: I’; where I’ is optionally substituted by one or more groups selected from: i) nitro; ii) nitroso; iii) (O)2S(O - )-, M + ; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X’-; viii) R°-X’-C(X)- and ix) R°-X’-C(X)-X’’; where M + , R°, X, X’ and X’’ are as previously defined;

[0423] In particular, R 37 to R 40 represent a hydrogen atom, and R 41 to R 44 may be the same or different and represent hydroxy or (O)2S(O - )-, M + ; and when R 43 and R 44 together form a benzo group, it is preferably substituted by an (O)2S(O - )- group;

[0424] It should be understood that at least one of the rings G, H, I or I’ contains at least one sulfonic acid group (O)2S(O - )- or a carboxylic acid group -C(O)O - ; preferably sulfonate.

[0425] As examples of dyes of formula (XXIII), mention may be made of: Acid Blue 1; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 3; Acid Green 5 and Acid Green 50.

[0426] f) Xanthene-based dyes of formula (XXIV):

[0427]

[0428] In formula (XXIV):

[0429] -R 45 , R 46 , R 47 and R 48 may be the same or different and represent hydrogen or halogen atoms;

[0430] -R 49 , R 50 , R 51 and R 52 may be the same or different and represent a hydrogen or halogen atom, or a group selected from the following:

[0431] -alkyl;

[0432] - alkoxy, alkylthio;

[0433] -Hydroxy, thiol;

[0434] -Nitro, nitroso;

[0435] -(O)2S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;

[0436] -(O)CO - -,M + , where M + As previously defined;

[0437] In particular, R 49 , R 50 , R 51 and R 52 represents a hydrogen or halogen atom;

[0438] -G represents an oxygen or sulfur atom or a group NRe, wherein Re is as defined previously; in particular, G represents an oxygen atom;

[0439] -L represents alkoxide O - ,M + ; Thiol salt S - ,M + or a group NRf, wherein Rf represents a hydrogen atom or an alkyl group, and M +As defined above; M + especially sodium or potassium;

[0440] -L' represents oxygen or sulfur atom or ammonium group: N + RfRg, wherein Rf and Rg may be identical or different, represent a hydrogen atom or an optionally substituted alkyl or aryl group; L' represents in particular an oxygen atom or an optionally substituted alkyl or aryl group by one or more alkyl groups or (O) m S(O - )-,M + A phenylamino group substituted with a group, wherein m and M + As previously defined;

[0441] - Q and Q' may be the same or different and represent an oxygen or sulfur atom; in particular, Q and Q' represent an oxygen atom;

[0442] -M + As defined previously.

[0443] As examples of dyes of formula (XXIV), mention may be made of: Acid Yellow 73; Acid Red 51; Acid Red 52; Acid Red 87; Acid Red 92; Acid Red 95; Acid Violet 9;

[0444] g) Indole-based dyes of formula (XXV):

[0445]

[0446] In formula (XXV):

[0447] -R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 and R 60 may be the same or different and represent a hydrogen atom or a group selected from the following:

[0448] -alkyl;

[0449] - alkoxy, alkylthio;

[0450] -Hydroxy, thiol;

[0451] -Nitro, nitroso;

[0452] -R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"-, wherein R° represents a hydrogen atom or an alkyl group or an aryl group; X, X' and X" may be the same or different and represent an oxygen or sulfur atom, or NR, wherein R represents a hydrogen atom or an alkyl group;

[0453] -(O)2S(O- )-,M + , where M + represents a hydrogen atom or a cationic counterion;

[0454] -(O)CO - )-,M + , where M + is as previously defined;

[0455] -G represents an oxygen or sulfur atom or the group NRe, where Re is as previously defined; in particular, G represents an oxygen atom;

[0456] -Ri and Rh may be the same or different and represent a hydrogen atom or an alkyl group;

[0457] It should be understood that formula (XXIII) contains at least one sulfonate group (O)2S(O - )-,M + or a carboxylate group -C(O)O - ,M + ; preferably sodium sulfonate.

[0458] As an example of the dye of formula (XXV), Acid Blue 74 can be mentioned;

[0459] h) Quinoline-based dyes of formula (XXVI):

[0460]

[0461] In formula (XXVI):

[0462] -R 61 represents a hydrogen or halogen atom or an alkyl group;

[0463] -R 62 , R 63 and R 64 may be the same or different and represent a hydrogen atom or the group (O)2S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;

[0464] Alternatively, R 61 and R 62 , or R 61 and R 64 together form a benz group, which is optionally substituted by one or more groups (O)2S(O - )-,M + , where M + represents a hydrogen atom or a cationic counterion;

[0465] It should be understood that formula (XXVI) contains at least one sulfonate group (O)2S(O - )-, M + , preferably sodium sulfonate.

[0466] As examples of the dyes of formula (XXVI), mention may be made of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

[0467] Among the natural direct dyes that can be used according to the present invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, gallic acid, protocatechaldehyde, indigo, indigo carmine, curcumin, mycophenolic acid, apigenidin and orcein. Extracts or decoctions containing these natural dyes can also be used and in particular poultices or extracts based on henna.

[0468] Preferably, the direct dye is selected from anionic direct dyes.

[0469] The colorant can be present in a total amount ranging from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight relative to the total weight of composition C; preferably, the colorant is selected from pigments.

[0470] The pigment can be present in a total amount ranging from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight and still better from 0.5% to 10% by weight relative to the total weight of composition C.

[0471] The direct dye can be present in a total amount ranging from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight relative to the total weight of composition C.

[0472] Compound containing at least one carboxyl functional group

[0473] Composition C used in the context of the method according to the present invention may also contain at least one compound containing at least one carboxyl functional group.

[0474] Preferably, composition C used in the context of the method according to the present invention contains at least one compound containing at least one carboxyl functional group.

[0475] Preferably, the compound containing at least one carboxyl functional group is selected from silicone compounds containing at least one carboxyl, polyurethanes, acrylic polymers and mixtures thereof.

[0476] Polyurethane and acrylic polymer

[0477] According to a preferred embodiment, composition C comprises at least one compound containing at least one carboxyl functional group selected from polyurethanes, acrylic polymers and mixtures thereof.

[0478] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of polymer particles selected from polyurethanes, acrylic polymers and mixtures thereof.

[0479] Preferably, composition C comprises at least one compound containing at least one carboxyl functional group in the form of an aqueous dispersion of particles of polyurethanes, acrylic polymers and mixtures thereof.

[0480] The dispersion can be a simple dispersion in the aqueous medium of the cosmetic composition. As a particular case of the dispersion, mention may be made of latex.

[0481] The aqueous dispersion of polymer particles may be selected from the aqueous dispersion of polyurethane particles.

[0482] More particularly, the polyurethane present in the aqueous dispersion used in the present invention is produced by the reaction of:

[0483] - a prepolymer of the following formula (A):

[0484]

[0485] wherein:

[0486] - R1 represents a divalent group of a dihydroxylated compound;

[0487] - R2 represents a group of an aliphatic or cycloaliphatic polyisocyanate;

[0488] - R3 represents a group of a low molecular weight diol, optionally substituted by one or more ionic groups;

[0489] - n represents an integer ranging from 1 to 5, and

[0490] - m is greater than 1;

[0491] - at least one chain extender according to the following formula (B):

[0492] H2N-R4-NH2 (B),

[0493] where R4 represents an alkylene or alkyleneoxy not substituted by one or more ionic or potentially ionic groups; and

[0494] - at least one chain extender according to the following formula (C):

[0495] H2N-R5-NH2 (C),

[0496] Wherein R5 represents an alkylene group substituted by one or more ionic or potentially ionic groups.

[0497] Among the dihydroxylated compounds that can be used according to the present invention, mention may be made in particular of compounds containing two hydroxyl groups and having a number average molecular weight of from about 700 to about 16,000, and preferably from about 750 to about 5000. By way of example of dihydroxylated compounds having a high molecular weight, mention may be made of polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, polyhydroxylated polyacetates, polyhydroxylated polyacrylates, polyhydroxylated amide polyesters, polyhydroxylated polybutadienes, polyhydroxylated polysulfides, and mixtures thereof. Preferably, the hydroxylated compounds are selected from polyol polyesters, polyol polyethers, polyhydroxylated polycarbonates, and mixtures thereof.

[0498] The polyisocyanates that can be used according to the present invention are especially selected from organic diisocyanates having a molecular weight of from about 112 to 1000, and preferably from about 140 to 400.

[0499] Preferably, the polyisocyanates are selected from diisocyanates and more particularly from those represented by the general formula R2(NCO)2, where R2 represents a divalent aliphatic hydrocarbon-based group containing 4 to 18 carbon atoms, a divalent cycloaliphatic hydrocarbon-based group containing 5 to 15 carbon atoms, a divalent araliphatic hydrocarbon-based group containing 7 to 15 carbon atoms, or a divalent aromatic hydrocarbon-based group containing 6 to 15 carbon atoms.

[0500] Preferably, R2 represents an organic diisocyanate. As examples of organic diisocyanates, the following may be especially selected: tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate (isophorone diisocyanate or IPDI), bis(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanato-3-methylcyclohexyl)methane, isomers of toluene diisocyanate (TDI) such as toluene 2,4-diisocyanate, toluene 2,6-diisocyanate and mixtures thereof, hydrogenated toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures with its isomers 2,4-diphenylmethane diisocyanate and optionally 2,2'-diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, and mixtures thereof.

[0501] Preferably, the diisocyanate is an aliphatic and cycloaliphatic diisocyanate, and more preferably is selected from 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, and mixtures thereof.

[0502] According to the present invention, the term "low molecular weight diol" refers to diols having a molecular weight of from about 62 to 700, and preferably from 62 to 200. These diols can contain aliphatic, cycloaliphatic or aromatic groups. Preferably, they contain only aliphatic groups.

[0503] Preferably, R3 represents a low molecular weight diol containing more than 20 carbon atoms, more preferably selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, butylethylpropanediol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), and mixtures thereof.

[0504] The low molecular weight diol can optionally contain ionic or potentially ionic groups. Examples of low molecular weight diols containing ionic or potentially ionic groups are particularly described in patent US 3,412,054. Such compounds are preferably selected from dimethylolbutyric acid, dimethylolpropionic acid, carboxyl-containing polycaprolactone diols, and mixtures thereof.

[0505] If a low molecular weight diol containing ionic or potentially ionic groups is used, it is preferably used in an amount such that less than 0.30 meq of COOH / gram of polyurethane is present in the polyurethane dispersion.

[0506] The prepolymer is chain-extended by two families of chain extenders. The first class of chain extenders corresponds to compounds of formula (B).

[0507] The chain extenders of formula (B) are preferably selected from alkylene diamines such as hydrazine, ethylenediamine, propylenediamine, 1,4-butanediamine, piperazine; alkylene diamine oxides such as 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine (also known as dipropylamine diethylene glycol or DPA-DEG, available from Tomah Products, Milton, Wisconsin), 2-methyl-1,5-pentanediamine (Dytec A from DuPont), hexamethylenediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), ether amines of the DPA series available from Tomah Products, Milton, Wisconsin, such as dipropylamine propylene glycol, dipropylamine dipropylene glycol, dipropylamine tripropylene glycol, dipropylamine poly(propylene glycol), dipropylamine ethylene glycol, dipropylamine poly(ethylene glycol), dipropylamine 1,3-propylene glycol, dipropylamine 2-methyl-1,3-propylene glycol, dipropylamine 1,4-butanediol, dipropylamine 1,3-butanediol, dipropylamine 1,6-hexanediol, and dipropylamine cyclohexane-1,4-dimethanol; and mixtures thereof.

[0508] The second type of chain extender corresponds to compounds of general formula (C). Such compounds preferably have ionic or potentially ionic groups and two groups capable of reacting with isocyanate groups. Such compounds may optionally contain two groups capable of reacting with isocyanate groups and one group that is an ionic group or capable of forming an ionic group.

[0509] The ionic or potentially ionic groups may preferably be selected from tertiary ammonium or quaternary ammonium groups or groups that can be converted into such groups, carboxyl groups, carboxylate groups, sulfonic acid groups, and sulfonate groups. At least partial conversion of groups that can be converted into salts of tertiary ammonium or quaternary ammonium groups may be carried out before or during mixing with water.

[0510] The chain extender of formula (C) is preferably selected from diamino sulfonates, such as the sodium salt of N-(2-aminoethyl)-2-aminoethanesulfonic acid (ASA), the sodium salt of N-(2-aminoethyl)-2-aminopropionic acid, and mixtures thereof.

[0511] The polyurethane that can be used according to the present invention may also optionally contain compounds (chain terminators) located at the chain ends and terminating the chain. Such compounds are particularly described in patents US 7 445 770 and / or US 7 452 770.

[0512] Preferably, the aqueous dispersion of polyurethane particles has a viscosity at 23 °C of less than 2000 mPa·s, more preferably less than 1500, and still better less than 1000. Even more preferably, the aqueous polyurethane dispersion has a glass transition temperature below 0 °C.

[0513] Also preferably, based on the weight of the dispersion, the aqueous polyurethane dispersion has a polyurethane (or active material, or solid) content by weight of from 20% to 60%, more preferably by weight from 25% to 55%, and still better by weight from 30% to 50%. This is intended to mean that the polyurethane content (dry matter) of the aqueous dispersion is preferably from 20% to 60% by weight, more preferably from 25% to 55% by weight, and still better from 30% to 50% by weight relative to the total weight of the dispersion.

[0514] Also preferably, the aqueous dispersion of polyurethane particles has a glass transition temperature (Tg) of less than or equal to -25 °C, preferably less than -35 °C, and more preferably less than -40 °C.

[0515] The polyurethane particles may have an average diameter ranging up to about 1000 nm, for example from about 50 nm to about 800 nm, and still better from about 100 nm to about 500 nm. These particle sizes can be measured using a laser particle size analyzer (such as Brookhaven BI90).

[0516] As non-limiting examples of aqueous polyurethane dispersions, mention may be made of those sold by Bayer under the name , such as C1000 (INCI name: Polyurethane-34), C1001 (INCI name: Polyurethane-34), C1003 (INCI name: Polyurethane-32), C1004 (INCI name: Polyurethane-35) and C1008 (INCI name: Polyurethane-48).

[0517] Also mention may be made of the following aqueous polyurethane dispersions: isophthalic acid / adipic acid copolymer / hexanediol / neopentyl glycol / dimethylolpropionic acid / isophorone diisocyanate (INCI name: Polyurethane-1, such as PUR, BASF), polyurethanes of polycarbonates, polyurethanes of aliphatic polyesters and aliphatic polyurethanes (such as or DSM series, such as R989 and R-2202).

[0518] According to a preferred embodiment, the aqueous dispersion of polyurethane particles may be selected from the aqueous dispersion of particles of a compound having the INCI name Polyurethane-35 or a compound having the INCI name Polyurethane-34.

[0519] Preferably, the compound containing at least one carboxyl functional group is in the form of an aqueous dispersion of particles of an acrylic polymer, more preferably in the form of an aqueous dispersion of film-forming acrylic polymer particles.

[0520] For the purposes of the present invention, the term "polymer" means a compound corresponding to the repetition of one or more units (these units being derived from compounds called monomers). The unit or units are repeated at least twice and preferably at least three times.

[0521] The term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a macroscopically continuous film, and preferably an adhesive film, on a support, in particular on keratin hair fibers.

[0522] For the purposes of the present invention, the term "acrylic polymer" means a polymer synthesized from at least one monomer selected from (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide.

[0523] The units of (meth)acrylic monomers derived from the polymer may optionally be in the form of salts, in particular alkali metal salts, alkaline earth metal salts or ammonium salts, or organic base salts.

[0524] (Meth)acrylic acid ester (also known as (meth)acrylate) is preferably selected from alkyl (meth)acrylates, especially C1-C 30 alkyl esters, preferably C1-C 20 alkyl esters and more preferably C1-C 10 alkyl esters; aryl (meth)acrylates, especially C6-C 10 aryl esters; and hydroxyalkyl (meth)acrylates, especially C2-C6 hydroxyalkyl (meth)acrylates.

[0525] Among the alkyl (meth)acrylates, mention may be made of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate and cyclohexyl (meth)acrylate.

[0526] Among the hydroxyalkyl (meth)acrylates, mention may be made of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

[0527] Among the aryl (meth)acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

[0528] Particularly preferred (meth)acrylates are alkyl, preferably C1-C 30 , more preferably C1-C 20 , even more preferably C1-C 10 , and even more particularly C1-C4 alkyl (meth)acrylates.

[0529] According to the present invention, the alkyl group of the ester may be fluorinated or even perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms.

[0530] Examples of (meth)acrylamide that may be mentioned include (meth)acrylamide and also N-alkyl (meth)acrylamides, especially N-(C2-C 12 alkyl)(meth)acrylamides. Among the N-alkyl (meth)acrylamides that may be mentioned are N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide and N-undecylacrylamide.

[0531] The acrylic polymer according to the present invention may be a homopolymer or a copolymer, preferably a copolymer, and even more preferably a copolymer of (meth)acrylic acid and (meth)acrylate.

[0532] Preferably, the acrylic polymer according to the invention comprises one or more units derived from the following monomers:

[0533] a) (meth)acrylic acid; and

[0534] b) C1 to C 30 Preferably C1 to C 20 More preferably C1 to C 10 And even more particularly C1 to C4 alkyl (meth)acrylates.

[0535] Preferably, the aqueous dispersion of acrylic polymer particles does not contain any surfactant.

[0536] The term "surfactant" refers to any reagent capable of changing the surface tension between two surfaces.

[0537] Among the acrylic polymers according to the invention, mention may be made of copolymers of (meth)acrylic acid and (meth)methyl acrylate or (meth)ethyl acrylate, in particular the copolymer of methacrylic acid and ethyl acrylate, such as the compound sold by BASF under the trade name Luvimer MAE, or the polyacrylate-2 crosslinked polymer sold by Lubrizol under the trade name Fixate Superhold Polymer, or the acrylate copolymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000VP3, or the acrylate polymer sold by Daito Kasei Kogyo under the trade name Daitosol 3000SLPN-PE1.

[0538] The acrylic polymer may optionally contain one or more additional monomers other than (meth)acrylic acid and / or (meth)acrylate and / or (meth)acrylamide monomers.

[0539] As additional monomers, mention will be made, for example, of styrene monomers, in particular styrene and α-methylstyrene, and preferably styrene.

[0540] In particular, the acrylic polymer may be a styrene / (meth)acrylate copolymer, and in particular a polymer selected from the copolymers resulting from the polymerization of at least one styrene monomer and at least one C1 to C 20 alkyl (meth)acrylate, preferably C1 to C 10 alkyl (meth)acrylate monomer.

[0541] (meth)acrylic acid C1 to C 10The alkyl ester monomer may be selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate.

[0542] As acrylic polymers, mention may be made of styrene / (meth)acrylate copolymers, which are sold by BASF under the name Joncryl 77, by Akzo Nobel under the name Yodosol GH41F, and by Interpolymer under the name Syntran 5760CG.

[0543] Preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle.

[0544] More preferably, composition C comprises an aqueous dispersion of at least one acrylic polymer particle, which comprises one or more units derived from the following monomers:

[0545] a) (Meth)acrylic acid; and

[0546] b) C1 to C 30 , more preferably C1 to C 20 , still better C1 to C 10 , and even more particularly C1 to C4 alkyl (meth)acrylates.

[0547] Preferably, based on the weight of the dispersion, the aqueous dispersion of acrylic polymer particles has an acrylic polymer (or active material, or solid) content of from 20% to 60% by weight, more preferably from 22% to 55% by weight, and still better from 25% to 50% by weight.

[0548] Silicone acrylate copolymer

[0549] According to a specific embodiment, the silicone compound containing at least one carboxyl group is selected from silicone acrylic copolymers.

[0550] Thus, according to a specific embodiment, the compound containing at least one carboxyl functional group is selected from silicone acrylic copolymers.

[0551] Preferably, the silicone acrylic copolymer comprises:

[0552] - at least one acrylic acid or methacrylic acid or crotonic acid unit; and

[0553] - at least one polydimethylsiloxane (PDMS) unit.

[0554] For the purposes of the present invention, according to what is commonly accepted, the term "polydimethylsiloxane" (also simply referred to as PDMS) denotes any silicone polymer or oligomer having a linear structure with variable molecular weight, which is obtained by polymerizing and / or polycondensing appropriately functionalized silanes and which consists essentially of repeating main units in which silicon atoms are linked together via oxygen atoms (siloxane bond Si-O-Si-), containing methyl groups directly linked to said silicon atoms via carbon atoms.

[0555] The PDMS chains that can be used to obtain the copolymers used according to the present invention contain at least one polymerizable group, which is preferably located at at least one end of the chain, i.e., the PDMS can contain, for example, polymerizable groups at each of the two ends of the chain or a polymerizable group at one end of the chain and a trimethylsilyl end group at the other end of the chain.

[0556] The term "polymerizable group" means a group capable of polymerizing with other polymerizable groups or monomers. Preferably, the polydimethylsiloxane unit contains at least one polymerizable group.

[0557] Preferably, the polymerizable group contains at least one vinyl group.

[0558] Preferably, the polydimethylsiloxane (PDMS) unit contains at least one polymerizable group containing at least one vinyl group, preferably at least two polymerizable groups containing at least one vinyl group, which are preferably located at at least one chain end.

[0559] As previously indicated, the silicone acrylic copolymer preferably contains at least one acrylic acid or methacrylic acid or crotonic acid unit, i.e., at least one unit containing a carboxyl group.

[0560] The term "carboxyl group" means COOH or COO - functional group, COO - The counterion of the group is preferably selected from alkali metals, alkaline earth metals and quaternary ammonium.

[0561] Preferably, the silicone acrylic copolymer contains:

[0562] - at least one acrylic acid or methacrylic acid or crotonic acid unit, and at least one acrylate or methacrylate or vinyl ester unit; and

[0563] - at least one polydimethylsiloxane (PDMS) unit.

[0564] More preferably, the composition contains one or more silicone acrylic copolymers, which contain:

[0565] - At least one crotonic acid unit and at least one unit selected from the following: crotonic acid alkyl ester units, wherein the alkyl is a straight-chain or branched-chain saturated group containing from 1 to 20 carbon atoms; vinyl acetate units; vinyl alkyl ester units, wherein the alkyl is a straight-chain or branched-chain saturated group containing from 2 to 20 carbon atoms; and mixtures thereof; and

[0566] - At least one polydimethylsiloxane (PDMS) unit.

[0567] The term "crotonic acid unit" means a unit derived from a crotonic acid monomer or its salt.

[0568] The term "crotonic acid alkyl ester unit" means a unit derived from a crotonic acid ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 1 to 20 carbon atoms.

[0569] The term "vinyl alkyl ester unit" means a unit derived from a vinyl ester monomer, which contains a saturated straight-chain or branched-chain alkyl group containing from 2 to 20 carbon atoms.

[0570] The term "vinyl acetate unit" means a unit derived from a vinyl acetate monomer.

[0571] According to a preferred embodiment, the silicone acrylic copolymer comprises:

[0572] - At least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (wherein the alkyl is a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms), and

[0573] - At least one polydimethylsiloxane (PDMS) unit, which preferably contains at least one polymerizable group containing at least one vinyl.

[0574] According to a particularly preferred embodiment, the silicone acrylic copolymer comprises:

[0575] - At least one crotonic acid unit, at least one vinyl acetate unit and at least one vinyl alkyl ester unit (wherein the alkyl is a straight-chain or branched-chain saturated group containing from 6 to 16 carbon atoms), and

[0576] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl.

[0577] More preferably, the composition comprises one or more silicone acrylic copolymers, which comprise:

[0578] - At least one crotonic acid unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit (wherein the alkyl is a saturated straight-chain or branched-chain group containing from 2 to 20 carbon atoms, preferably from 2 to 18 carbon atoms); and

[0579] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl.

[0580] Even more preferably, the composition contains one or more silicone acrylate copolymers, which contain:

[0581] - At least one crotonic acid unit, at least one vinyl acetate unit, and at least one vinyl alkyl ester unit (wherein the alkyl is a saturated straight-chain or branched-chain group containing from 6 to 16 carbon atoms); and

[0582] - At least one polydimethylsiloxane (PDMS) unit, which contains at least one polymerizable group containing at least one vinyl.

[0583] Among the silicone acrylate copolymers that can be used in the context of the present invention, mention may be made of the compound sold by Wacker Chemie AG under the trade name P1101, having the INCI name Crotonic Acid / Vinyl C8 - 12 Isalkyl Esters / VA / Bis-Vinyl Polydimethylsiloxane Crosspolymer.

[0584] The total amount of the compound containing at least one carboxyl functional group preferably ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight, and even more preferably from 2% to 10% by weight relative to the total weight of composition C.

[0585] The total amount of the aqueous dispersion of the particles of the polymer selected from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of composition C.

[0586] According to a specific embodiment, the total amount of the aqueous dispersion of the acrylic polymer particles preferably ranges from 0.1% to 40% by weight, more preferably from 0.5% to 30% by weight, still better from 1% to 25% by weight, and even more preferably from 2% to 20% by weight relative to the total weight of composition C.

[0587] Advantageously, the total amount of the silicone acrylate copolymer ranges from 0.1% to 30% by weight, more preferably from 0.5% to 20% by weight, still better from 1% to 15% by weight and even more preferably from 2% to 10% by weight, relative to the total weight of composition C.

[0588] Non-carboxylic acid anionic thickener

[0589] Composition C used in the context of the process according to the invention may also comprise at least one non-carboxylic acid anionic thickener.

[0590] For the purposes of the present invention, the term "non-carboxylic acid reagent" means a reagent that does not contain any carboxylic acid functional group (-COOH) or carboxylate functional group (-COO - )

[0591] For the purposes of the present invention, the term "thickener" means a compound that increases the viscosity of a composition into which it is introduced to a concentration of 0.05% by weight relative to the total weight of the composition by at least 20 cps, preferably at least 50 cps, at room temperature (25 °C), at atmospheric pressure and at a shear rate of 1 s -1 (the viscosity can be measured using a cone / plate viscometer, a Haake R600 rheometer, etc.).

[0592] Preferably, the non-carboxylic acid anionic thickener is selected from non-carboxylic acid anionic polymers, more preferably from anionic polymers carrying sulfonic acid groups.

[0593] For the purposes of the present invention, the term "anionic polymer" means a polymer that contains one or more anionic or anionizable groups and does not contain any cationic or cationizable groups.

[0594] Advantageously, the non-carboxylic acid anionic thickener is selected from anionic polymers comprising at least one ethylenically unsaturated monomer carrying a sulfonic acid group, in free form or in partially or fully neutralized form.

[0595] These polymers may be crosslinked or non-crosslinked. They are preferably crosslinked.

[0596] These polymers may be associative or non-associative, preferably non-associative.

[0597] It should be understood that an "associative polymer" is a polymer that is capable of associating reversibly with itself or with other molecules in an aqueous medium.

[0598] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0599] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, particularly from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms.

[0600] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecanol or decanol. It may also denote a hydrocarbon-based polymer such as polybutadiene.

[0601] The ethylenically unsaturated monomer carrying a sulfonic acid group is particularly selected from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C1-C 22 )alkylsulfonic acid, N-(C1-C 22 )alkyl(meth)acrylamido(C1-C 22 )alkylsulfonic acid such as undecylacrylamidomethanesulfonic acid and also its partially or fully neutralized forms.

[0602] More preferably, (meth)acrylamido(C1-C 22 )alkylsulfonic acid will be used, such as acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecanesulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and also its partially or fully neutralized forms.

[0603] Particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and also its partially or fully neutralized forms are used.

[0604] Among the copolymers of 2-acrylamido-2-methylpropanesulfonic acid, mention may be made of the partially or fully neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and acrylamide; in particular, mention may be made of the product described in Example 1 of EP 503 853, and reference may be made to said document regarding these polymers.

[0605] Also mention may be made of the copolymer of 2-acrylamido-2-methylpropanesulfonic acid or its salt and 2-hydroxyethyl acrylate, such as the compound sold by SEPPIC under the name Sepinov EMT 10 (INCI name: Hydroxyethyl Acrylate / Sodium Acryloyldimethyl Taurate Copolymer).

[0606] The associative AMPS polymers may in particular be selected from those obtained by copolymerization with C6-C 22Statistical associative AMPS polymers modified by reaction with n-mono- or di-n-alkylamines, and as described in patent application WO 00 / 31154, forming an integral part of the content of the specification. These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acid derivatives, such as their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0607] Preferred polymers of this family are selected from associative copolymers of AMPS and at least one ethylenically unsaturated hydrophobic monomer.

[0608] These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acid derivatives, especially their esters with monohydric alcohols or mono- or polyalkylene glycols, (meth)acrylamide, vinylpyrrolidone, or mixtures of these compounds.

[0609] These copolymers are described in particular in patent application EP-A 750 899, patent US 5 089 578 and in the following publication by Yotaro Morishima:

[0610] -Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (2000), 323-336;

[0611] -Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water asstudied by fluorescence and dynamic light scattering, Macromolecules, Vol. 33, No. 10, (2000), 3694-3704;

[0612] -Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: salt effects on rheological behavior - Langmuir, Vol. 16, No. 12, (2000) 5324 - 5332;

[0613] -Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 40(2), (1999), 220 - 221.

[0614] Among these polymers, mention may be made of:

[0615] -Crosslinked or non-crosslinked, neutralized or non-neutralized copolymers comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8 - C 16 ) alkyl (meth)acrylamide or (meth)acrylic acid (C8 - C 16 ) alkyl ester units, such as those described in patent application EP - A750 899;

[0616] -Terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C6 - C 18 ) alkylacrylamide units, such as those described in patent US - 5 089 578.

[0617] Also mention may be made of fully neutralized copolymers of AMPS and dodecyl methacrylate, as well as crosslinked and non-crosslinked copolymers of AMPS and n-dodecylmethacrylamide, such as those described in the Morishima article mentioned above.

[0618] Preferably, the non-carboxylic acid anionic thickener is selected from the sodium 2-acrylamido-2-methylpropanesulfonate / hydroxyethyl acrylate copolymer (INCI name: hydroxyethyl acrylate / sodium acryloyldimethyltaurate copolymer) sold by SEPPIC.

[0619] Advantageously, the total amount of the non-carboxylic acid anionic thickener ranges from 0.01% to 20% by weight, preferably from 0.1% to 10% by weight, more preferably from 0.1% to 5% by weight and even more preferably from 0.1% to 3% by weight relative to the total weight of composition C.

[0620] Associative polymer

[0621] Composition C according to the invention may further comprise at least one associative polymer different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners as previously defined.

[0622] It is to be understood that an "associative polymer" is a polymer capable of associating reversibly with each other or with other molecules in an aqueous medium.

[0623] Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region.

[0624] The term "hydrophobic group" means a group or polymer having a saturated or unsaturated, straight-chain or branched hydrocarbon-based chain containing at least 10 carbon atoms, preferably 10 to 30 carbon atoms, particularly 12 to 30 carbon atoms, and more preferably 18 to 30 carbon atoms.

[0625] Preferably, the hydrocarbon-based group is derived from a monofunctional compound. For example, the hydrophobic group can be derived from fatty alcohols such as stearyl alcohol, dodecanol or decanol. It can also denote a hydrocarbon-based polymer, such as polybutadiene.

[0626] The associative polymer can have nonionic, anionic, cationic or amphoteric properties.

[0627] Preferably, the associative polymer is selected from anionic associative polymers.

[0628] Among the associative polymers of the anionic type, mention may be made of:

[0629] -(a) Those comprising at least one hydrophilic unit and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an ethylenically unsaturated anionic monomer, even more particularly by a vinyl carboxylic acid and most particularly by acrylic acid or methacrylic acid or a mixture thereof.

[0630] Among these anion - associating polymers, those which are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and / or methacrylic acid, 5% to 60% by weight of lower alkyl (meth)acrylates, 2% to 50% by weight of fatty chain allyl ethers, and 0% to 1% by weight of a cross - linker, which is a well - known copolymerizable unsaturated poly - ethylenically unsaturated monomer, such as diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate, or methylene bisacrylamide.

[0631] Among the latter polymers, those which are most particularly preferred are cross - linked terpolymers of methacrylic acid, ethyl acrylate, and polyethylene glycol (10 EO) stearyl ether (steareth - 10), especially those sold by Ciba under the name Salcare SC and Salcare SC which are 30% aqueous emulsions of cross - linked terpolymers of methacrylic acid, ethyl acrylate, and allyl ether of steareth - 10 (40 / 50 / 10).

[0632] -(b) Those containing i) at least one hydrophilic unit of the unsaturated olefinic carboxylic acid type and ii) at least one hydrophobic unit of the type such as (C10 - C30) alkyl esters of unsaturated carboxylic acids.

[0633] The (C 10 -C 30 ) alkyl esters of unsaturated carboxylic acids which can be used in the present invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

[0634] For example, this type of anionic polymer is described and prepared according to patents US 3 915 921 and US 4 509 949.

[0635] Among this type of anion - associating polymers, those which will be used more particularly are those composed of 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of acrylic C 10 -C 30 alkyl esters (hydrophobic unit), and 0% to 6% by weight of a cross - linkable polymerizable monomer, or alternatively those composed of 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of acrylic C 10 -C 30Those composed of an alkyl ester (hydrophobic unit) and 0.1% to 0.6% by weight of a crosslinked polymerizable monomer, such as those described previously.

[0636] Among the above-mentioned polymers, those most particularly preferred according to the present invention are those sold by Goodrich under the trade name Pemulen Pemulen Carbopol And even more preferably Pemulen products sold, and products sold by Ciba under the name Coatex products.

[0637] Also mentionable is the acrylic acid / lauryl methacrylate / vinylpyrrolidone terpolymer sold by ISP under the name Acrylidone LM.

[0638] -(c) Maleic anhydride / C 30 -C 38 α-olefin / maleic acid alkyl ester terpolymer, such as the product sold by Newphase Technologies under the name Performa V product sold (maleic anhydride / C 30 -C 38 α-olefin / isopropyl maleate copolymer).

[0639] -(d) Acrylic acid terpolymer, which comprises:

[0640] i) Approximately 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid [A],

[0641] ii) Approximately 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer in addition to [A],

[0642] iii) Approximately 0.5% to 60% by weight of a nonionic mono-carbamate, which is a reaction product of a mono-surfactant and a monoethylenically unsaturated monoisocyanate,

[0643] such as those described in patent application EP-A-0 173 109, and more particularly the terpolymer described in Example 3, namely the methacrylic acid / methyl acrylate / behenyl dimethyl-m-isopropenylbenzyl isocyanate ethoxylated (40EO) terpolymer, as a 25% aqueous dispersion.

[0644] -(e) Copolymer, which contains among its monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkyleneated fatty alcohol.

[0645] Preferably, these compounds also contain an ester of an α,β-monoethylenically unsaturated carboxylic acid and a C1-C4 alcohol as a monomer.

[0646] Examples of compounds of this type that may be mentioned are those sold by Rohm and Haas Aculyn which is a terpolymer of methacrylic acid / ethyl acrylate / stearyl methacrylate oxyalkylated; and also Aculyn 88, which is also sold by Rohm and Haas.

[0647] Advantageously, the associative polymers that are different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously are selected from acrylic associative polymers, more preferably carboxylic acid acrylic associative polymers.

[0648] Particularly preferably, the associative polymers that are different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously are selected from copolymers that include, among their monomers, an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and an oxyalkylated fatty alcohol.

[0649] Advantageously, the total amount of the associative polymers that are different from the compounds containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickeners described previously ranges from 0.05% to 15% by weight, preferably from 0.05% to 10% by weight, more preferably from 0.1% to 5% by weight, and even more preferably from 0.1% to 1% by weight relative to the total weight of Composition C.

[0650] Organic solvent

[0651] Composition C according to the present invention may contain one or more organic solvents.

[0652] Examples of organic solvents that may be mentioned include C1-C4 lower alkanols such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, 1,2-hexanediol, propylene glycol, pentylene glycol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, and also aromatic alcohols (especially aromatic monohydric alcohols such as benzyl alcohol or phenoxyethanol), and mixtures thereof.

[0653] The organic solvent may be present in a total amount ranging from 0.01% to 60% by weight, preferably from 0.05% to 50% by weight, and more preferably from 0.1% to 45% by weight and including the end values relative to the total weight of Composition C.

[0654] The composition C used in the context of the method according to the invention can be aqueous. The water content can range from 1% to 90% by weight, preferably from 10% to 80% by weight and more preferably from 20% to 75% by weight, relative to the total weight of the composition C.

[0655] Additive

[0656] The composition C used in the context of the method according to the invention can contain any auxiliaries or additives customarily used.

[0657] Among the additives that can be included in the composition C, mention may be made of reducing agents, softening agents, defoaming agents, humectants, UV screening agents, peptizing agents, fragrances, anionic, cationic, nonionic or amphoteric surfactants, proteins, vitamins, polymers other than the polymers previously described, preservatives, silicones different from the compounds previously described, oils, waxes and mixtures thereof.

[0658] The composition C used in the context of the method according to the invention can in particular be in the form of a suspension, a dispersion, a gel, an emulsion, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion, or a multiple emulsion (W / O / W or polyol / O / W or O / W / O), in the form of a cream, a mousse, a stick, a vesicle dispersion, in particular a vesicle dispersion of ionic or non-ionic lipids, or a two-phase or multi-phase lotion.

[0659] A person skilled in the art can, based on their general knowledge, first consider the nature of the ingredients used, in particular their solubility in the carrier, and secondly the intended application of the composition, to select a suitable form of presentation, as well as its preparation method.

[0660] Scheme

[0661] The composition T as defined above can be used on wet or dry keratinous hair fibers, as well as on any type of keratinous hair fibers that are blond or brown, natural or dyed, permanently waved, bleached or relaxed.

[0662] Preferably, a rinsing step is carried out after the application of the composition T as previously defined.

[0663] This rinsing step can be followed by a draining and / or drying step.

[0664] The composition T can be applied at room temperature (between 15 °C and 25 °C).

[0665] After the application of the composition T, it is possible to wait between 1 minute and 12 hours, particularly between 1 minute and 10 hours, more particularly between 1 minute and 7 hours, and more preferably between 1 minute and 6 hours, before applying the composition C to the keratinous hair fibers.

[0666] The composition C described above can be used on wet or dry keratin hair fibers, as well as on any type of keratin hair fibers that are blond or brown, natural or dyed, permanently waved, bleached or relaxed.

[0667] Preferably, a washing, rinsing, draining or drying step is carried out after applying the composition C to the keratin hair fibers.

[0668] More preferably, a drying step is carried out after applying the composition C to the keratin hair fibers.

[0669] The application of the composition C to the keratin hair fibers can be carried out by any conventional means, in particular using a comb, a fine brush, a coarse brush, a sponge or with the fingers.

[0670] The application of the composition C to the keratin hair fibers is generally carried out at room temperature (between 15 °C and 25 °C).

[0671] After applying the composition C to the keratin hair fibers, it is possible to wait between 1 minute and 6 hours, particularly between 1 minute and 2 hours, more particularly between 1 minute and 1 hour, and more preferably between 1 minute and 30 minutes, before, for example, a washing, rinsing, draining and / or drying step.

[0672] After applying the composition C, the keratin hair fibers can be left to dry or can be dried, for example, at a temperature greater than or equal to 30 °C.

[0673] Thus, the method according to the invention can include a step of applying heat to the keratin hair fibers using a heating tool.

[0674] The heat application step of the method according to the invention can be carried out using a hood, a hair dryer, a straightener, a curler, a Climazon hood, etc.

[0675] Preferably, the heat application step of the method according to the invention is carried out using a hair dryer.

[0676] When the method according to the invention involves a step of applying heat to the keratin hair fibers, the step of applying heat to the keratin hair fibers is carried out after applying the composition C to the keratin hair fibers.

[0677] During the step of applying heat to the keratin hair fibers, a mechanical action can be exerted on the tresses, such as combing, brushing or passing the fingers through.

[0678] When the step of applying heat to the keratin hair fibers is carried out using a hood or a hair dryer, the temperature is preferably between 30 °C and 110 °C, preferably between 50 °C and 90 °C.

[0679] When the step of applying heat to the keratin hair fibers is carried out using a straightener, the temperature is preferably between 110°C and 220°C, preferably between 140°C and 200°C.

[0680] In a particular variant, the method of the invention involves a step (c1) of applying heat using a hood, a hair dryer or a Climazon hood, preferably a hair dryer, and a step (c2) of applying heat using a straightener or a curler, preferably a straightener.

[0681] Step (c1) can be carried out before step (c2).

[0682] During step (c1), also known as the drying step, the keratin hair fibers can be dried, for example, at a temperature above or equal to 30°C. According to a particular embodiment, this temperature exceeds 40°C. According to a particular embodiment, this temperature exceeds 45°C and is lower than 110°C.

[0683] Preferably, if the keratin hair fibers are dried, in addition to supplying heat, they are dried with an air flow. This air flow during drying makes it possible to improve the strand separation of the coating.

[0684] During drying, a mechanical action can be exerted on the tresses, such as combing, brushing or passing the fingers through.

[0685] During step (c2), the passage of the straightener or the curler, preferably the straightener, can be carried out at a temperature ranging from 110°C to 220°C, preferably between 140°C and 200°C.

[0686] After the heating step, a shaping step can be carried out, for example using a straightener; the temperature for the shaping step can be between 110°C and 220°C, preferably between 140°C and 200°C.

[0687] Preferably, the invention is a method for dyeing keratin hair fibers, the method comprising the following steps:

[0688] i) applying composition T to the keratin hair fibers, the composition comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant as previously described and a silicone in an amount of less than 1% by weight relative to the total weight of composition T; and preferably composition T that does not contain any silicone;

[0689] ii) a step of rinsing, draining and / or drying said keratin hair fibers; and then

[0690] iii) applying to the keratin hair fibers at least one composition C, the composition comprising:

[0691] - at least one (poly)carbodiimide compound as previously described; and

[0692] - at least one colorant selected from pigments, direct dyes and mixtures thereof as previously described; and then

[0693] iv) optionally allowing the composition C to have a residence time on these keratinous hair fibers of from 1 minute to 30 minutes, preferably from 1 to 20 minutes; and then

[0694] v) optionally washing, rinsing, draining and / or drying the keratinous hair fibers.

[0695] Preferably, composition T comprises at least one anionic surfactant.

[0696] Advantageously, composition T comprises at least one anionic surfactant and at least one amphoteric or zwitterionic surfactant.

[0697] Preferably, composition C further comprises at least one compound containing at least one carboxyl functional group as previously described.

[0698] Preferably, composition C further comprises at least one non-carboxylic acid anionic thickener as previously described, preferably selected from (meth)acrylamido(C1-C 22 )alkylsulfonic acid.

[0699] Preferably, composition C further comprises at least one associative polymer different from the compound containing at least one carboxyl functional group as described above and different from the non-carboxylic acid anionic thickener as previously defined, preferably an acrylate associative polymer.

[0700] Advantageously, the step of applying composition C to the keratinous hair fibers is repeated several times.

[0701] According to a preferred embodiment, step b) comprises instantaneously mixing at least two compositions A and B at the time of use to obtain composition C and comprises applying composition C to the keratinous hair fibers, wherein:

[0702] - composition A comprises at least one (poly)carbodiimide compound as previously defined;

[0703] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes and mixtures thereof as previously defined.

[0704] Advantageously, composition C or composition B comprises at least one compound containing at least one carboxyl functional group, which is preferably selected from silicone compounds containing at least one carboxyl, polyurethanes, acrylic polymers and mixtures thereof.

[0705] Preferably, composition B comprises at least one compound containing at least one carboxyl functional group, which is preferably selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers, and mixtures thereof.

[0706] According to a preferred embodiment, step b) comprises instantaneously mixing at least two compositions A and B at the time of use to obtain composition C and comprises applying composition C to the keratinous hair fibers, wherein:

[0707] - Composition A comprises at least one (poly)carbodiimide compound as previously defined;

[0708] - Composition B comprises at least one compound containing at least one carboxyl functional group as previously described;

[0709] Composition A and / or composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof as previously defined.

[0710] Composition A and / or composition B may optionally comprise at least one non-carboxylic acid anionic thickener as previously described and / or at least one associative polymer different from the compound containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickener as previously defined.

[0711] Advantageously, composition A comprises at least one non-carboxylic acid anionic thickener as previously described.

[0712] Advantageously, composition B comprises at least one compound containing at least one carboxyl functional group as previously described and / or at least one associative polymer different from the compound containing at least one carboxyl functional group and different from the non-carboxylic acid anionic thickener as previously defined.

[0713] Preferably, composition B comprises at least one colorant selected from pigments, direct dyes, and mixtures thereof as previously described, and composition A does not comprise any colorant selected from pigments, direct dyes, and mixtures thereof as previously described, or comprises an amount such that it does not permit the keratinous hair fibers to be dyed, and more preferably does not comprise any colorant selected from pigments, direct dyes, and mixtures thereof as previously described.

[0714] According to this embodiment, compositions A and B are preferably mixed less than 15 minutes, more preferably less than 10 minutes, still better less than 5 minutes before application to the keratinous hair fibers.

[0715] The weight ratio between Composition A and Composition B preferably ranges from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.5 to 2, or even from 0.6 to 1.5. In a specific embodiment, the weight ratio between Composition A and Composition B is equal to 1.

[0716] (Poly)carbodiimide compounds preferably range from 0.01% to 40% by weight, more preferably from 0.1% to 30% by weight, still more preferably from 0.5% to 20% by weight, and even more preferably from 1% to 12% by weight, based on the total weight of Composition A.

[0717] Compounds containing at least one carboxyl functional group preferably range from 0.2% to 60% by weight, more preferably from 1% to 40% by weight, still more preferably from 1% to 30% by weight, and even more preferably from 2% to 20% by weight, based on the total weight of Composition B.

[0718] The total amount of the aqueous dispersion of particles of polymers selected from polyurethanes, acrylic polymers, and mixtures thereof preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 50% by weight, still more preferably from 1% to 40% by weight, and even more preferably from 2% to 30% by weight, based on the total weight of Composition B.

[0719] According to a specific embodiment, the total amount of the aqueous dispersion of acrylic polymer particles preferably ranges from 0.2% to 60% by weight, more preferably from 1% to 50% by weight, still more preferably from 1% to 40% by weight, and even more preferably from 2% to 30% by weight, based on the total weight of Composition B.

[0720] The present invention will now be described more specifically by way of examples, which do not limit the scope of the invention in any way. However, these examples enable the support of specific features, variants, and preferred embodiments of the invention.

[0721] Examples

[0722] The (poly)carbodiimides of the present invention are obtainable from commercial products or reagents which can be synthesized according to chemical reactions known to those skilled in the art by synthesis methods known to those skilled in the art. For example, reference may be made to the book Sciences of Synthesis - Houben - Weyl Methods of Molecular Transformations, 2005, Georg Thiem Verlag Kg, Rudigerstrasse 14, D - 70469 Stuttgart, or US Patent US 4 284 730 or Canadian Patent Application CA 2 509 861.

[0723] More specifically, the method for preparing the (poly)carbodiimides of the present invention involves, in a first step, a diisocyanate reagent (1):

[0724] O=C=N - L1 - N=C=O (1),

[0725] In formula (1), L1 is as previously defined. In the presence of a carboimidation catalyst (2) (such as those described in US 4 284 730, especially phosphorus - based catalysts, particularly selected from cyclophosphene oxides and cyclophosphene sulfoxides, diaza - and oxa - phospholanes), preferably under an inert atmosphere (nitrogen or argon), and especially in a polar solvent (preferably an aprotic solvent such as THF, diglyme, triglyme, 1,4 - dioxane or DMF), at a temperature between room temperature and the reflux temperature of the solvent, preferably at about 140 °C, a reaction is carried out to obtain a carbodiimide diisocyanate compound (3):

[0726] O=C=N - L1 - (N=C=N - L1) n - N=C=O (3),

[0727] In formula (3), L1 and n are as previously defined. A benzoyl halide such as benzoyl chloride may be added to deactivate the catalyst.

[0728] In order to obtain a "symmetric" (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of a nucleophilic reagent R1 - X1 - H, and then with 0.5 equivalent of the reagent H - E - H, where R1, X1 and E are as previously defined, to obtain a "symmetric" compound (4) according to the present invention:

[0729] [R1 - X1 - C(O) - NH - L1 - (N=C=N - L1) n-NH-C(O)]2-E (4),

[0730] In formula (4), R1, X1, L1, n and E are as defined previously. According to a variant of obtaining compound (4) from (3), 0.5 equivalents of the reagent H-E-H can be added first, and then 1 equivalent of the reagent R1-X1-H can be added.

[0731] To obtain an “asymmetric” (poly)carbodiimide, during the second step of the preparation method, compound (3) is reacted with 1 molar equivalent (1 equivalent) of the nucleophilic reagent R1-X1-H, and then with 1 equivalent of the reagent H-E-H, where R1, X1 and E are as defined previously, to obtain compound (5):

[0732] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-H (5),

[0733] In formula (5), R1, X1, L1, n and E are as defined previously.

[0734] According to a variant of obtaining compound (5) from (3), 1 equivalent of the reagent R1-X1-H can be added first, and then 0.5 equivalent of the reagent H-E-H can be added.

[0735] During the third step, compound (5) is reacted with 1 equivalent of compound (6)

[0736] R2-X2-C(O)-NH-L1-(N=C=N-L1) z -N=C=O(6), and the compound (6) is prepared in advance from compound (3’):

[0737] O=C=N-L1-(N=C=N-L1) z -N=C=O(3’),

[0738] In formula (3’), L1 and z are as defined previously, and it is reacted with 1 equivalent of the nucleophilic reagent R2-X2-H, where L1, R2, X2 and z are as defined previously, to obtain the asymmetric compound (7):

[0739] R1-X1-C(O)-NH-L1-(N=C=N-L1) n -NH-C(O)-E-C(O)-NH-L1-(N=C=N-L1) z -NH-C(O)-X2-R2 (7),

[0740] In formula (7), R1, X1, L1, R2, X2, n, z and E are as defined previously.

[0741] 1 molar equivalent of the compound O═C═N-L1-(N═C═N-L1) z -N═C═O (3’) can be reacted with 1 / w molar equivalent of H-E-H, and then with 1 equivalent of the nucleophile R2-X2-H to obtain the compound (8):

[0742] H-[E-C(O)-NH-L1-(N═C═N-L1) z w -NH-C(O)-X2-R2 (8),

[0743] In formula (8), L1, R2, X2, z and E are as defined previously, and w is an integer between 1 and 3; more preferably, w = 1.

[0744] Then this final compound (8) can be reacted with 1 equivalent of the compound (4’):

[0745] R1-X1-C(O)-NH-L1-(N═C═N-L1) n -N═C═O (4’), (the compound (4’) can be synthesized by reacting 0.5 equivalent of the nucleophile R1-X1-H with 1 equivalent of the compound (3)), to obtain the (poly)carbodiimide (9) of the present invention:

[0746] R1-X1-C(O)-NH-L1-(N═C═N-L1) n -NH-C(O)-[E-C(O)-NH-L1-(N═C═N-L1) z w -NHC(O)-X2-R2 (9),

[0747] In formula (9), L1, R1, X1, R2, X2, n, z, w and E are as defined previously.

[0748] (Poly)carbodiimide compounds and similarly all reaction intermediates and reagents can be purified via conventional methods known to those skilled in the art, such as extraction with water and water-immiscible organic solvents, precipitation, centrifugation, filtration and / or chromatography.

[0749] Example 1: Method for synthesizing (poly)carbodiimide compounds

[0750] 50 g of 4,4’-dicyclohexylmethane diisocyanate and 0.5 g of 4,5-dihydro-3-methyl-1-phenyl-1H-phospholene 1-oxide were placed in a 500 mL three-necked round-bottom flask equipped with a thermometer, a stirrer and a reflux tube under stirring.

[0751] ​​The reaction medium was heated under nitrogen at 140 °C for 4 h, and the reaction was monitored by infrared spectroscopy by means of the absorption of isocyanate functional groups between 2200 and 2300 cm -1 and then cooled to 120 °C.

[0752] A mixture of 5.3 g of polyethylene glycol monomethyl ether and 1.2 g of 1,4-butanediol was introduced into the reaction medium with stirring. The temperature of 120 °C was maintained until the isocyanate functional groups had completely disappeared, monitored by infrared spectroscopy at 2200 - 2300 cm -1 and then cooled to room temperature.

[0753] After cooling to room temperature, the reaction medium was poured dropwise into a 500 mL glass beaker containing 85 g of distilled water with vigorous stirring to obtain the desired product in the form of a translucent yellow liquid.

[0754] Example 2

[0755] Compositions T1 and T2 as described in Table 1 below were prepared: Unless otherwise mentioned, amounts are expressed as g of active material as obtained / 100 g.

[0756] [Table 1]

[0757]

[0758] (1) Sold by Wacker under the name Belsil DADM 5050E

[0759] * Amount of starting material

[0760] Compositions A and B as described in Tables 2 and 3 below were also prepared: Unless otherwise mentioned, amounts are expressed as g of starting material as obtained / 100 g.

[0761] [Table 2]

[0762]

[0763] (2) Synthesis was carried out according to the synthetic method described in Example 1 (40% active material in water),

[0764] (3) Sold by Ciba under the name Sepinov EMT10 (90% active material).

[0765] [Table 3]

[0766]

[0767] (4) Sold by Daito Kasei Kogyo Co., Ltd. under the trade name Daitosol 3000SLPN-PE1 (aqueous dispersion containing 30% active material)

[0768] (5) Sold by Rohm and Haas under the trade name Aculyn (an alkoxylated methacrylic acid / ethyl acrylate / stearyl methacrylate terpolymer containing 30% active material)

[0769] (6) Sold by Dow Corning under the trade name Dow Corning HMW 2220 nonionic emulsion (a divinyl polydimethylsiloxane / polydimethylsiloxane block copolymer as an aqueous emulsion) (containing 60% active material)

[0770] Then, Composition A and Composition B are mixed at a mass ratio of 50 / 50 to obtain Composition C according to the present invention.

[0771] Scheme

[0772] First, Composition T1 or T2 is applied to tresses of moderately sensitized keratin hair fibers (20% alkali solubility). Each of these compositions is applied to the tresses of keratin hair fibers at a rate of 0.8 g of composition per gram of tress. Then, the tresses are rinsed, detangled, and dried with a hair dryer.

[0773] Then, Composition C is applied to the tresses previously treated with Composition T1 or Composition T2 at a rate of 0.8 g of composition per gram of tress. Then, the tresses of keratin hair fibers are detangled and dried with a hair dryer.

[0774] Therefore, the method of using Composition T1 and then using Composition C is a comparative method. Hereinafter, it is referred to as Method P1.

[0775] Therefore, the method of using Composition T2 and then using Composition C is the method according to the present invention. Hereinafter, it is referred to as Method P2.

[0776] The applied methods are summarized in Table 4 below:

[0777] [Table 4]

[0778] Method P1 (comparison) P2 (the present invention) Application of the composition T1 + C T2 + C

[0779] Then, the tresses of keratin hair fibers treated by Methods P1 and P2 are subjected to a test including several repeated shampoo washings in order to evaluate the tolerance (persistence) of the obtained coloring with respect to the shampoo washing according to the shampoo washing protocol described below.

[0780] Shampoo washing scheme:

[0781] Comb the tress of dyed keratin hair fibers, moisten it with water at 35 °C and then pass it through the fingers five times for 5 seconds. Then squeeze the tress of keratin hair fibers dry between two fingers.

[0782] Apply the standard shampoo (Garnier Ultra Doux) evenly to the dyed tress at a ratio of 0.4 g of standard shampoo per gram of tress, and gently massage the tress of keratin hair fibers for 15 seconds along the length from the root to the tip (6 passes).

[0783] Then place the tress of keratin hair fibers on a petri dish and let it stand for 1 minute.

[0784] Next, rinse the tress while passing it through the fingers (15 passes). Then squeeze the tress of keratin hair fibers dry between two fingers and then proceed with the next shampoo wash.

[0785] After conducting the shampoo wash test several times, comb and dry the tress of keratin hair fibers with a hair dryer.

[0786] Result

[0787] Evaluate the color fastness of the tress using a Minolta CM3610A spectrophotometer (light source D65, angle 10°, including specular reflection component) in the CIE L*a*b* system.

[0788] In this L*a*b* system, L* represents the intensity of the color, a* represents the green / red axis, and b* represents the blue / yellow axis.

[0789] Evaluate the color fastness of the coloring by the color difference ΔE between the measurements taken on the dyed tress before the shampoo wash test and then after undergoing five shampoo washes according to the protocol described above.

[0790] Calculate the ΔE value according to the following equation:

[0791]

[0792] In this equation, L*, a*, and b* represent the values measured after dyeing the keratin hair fibers and after the shampoo wash, and L0*, a0*, and b0* represent the values measured after dyeing the keratin hair fibers but before the shampoo wash.

[0793] [Table 6]

[0794]

[0795] Locks of keratinous hair fibers washed by means of process P2 according to the invention and washed with five shampoos have a significantly lower color difference ΔE than locks of keratinous hair fibers treated by a comparative process P1.

[0796] Thus, the colored coating obtained by means of the process according to the invention shows an improved persistence with respect to shampoo washing.

Claims

1. A method for dyeing keratinous hair fibers, the method comprising: a) applying to the keratinous hair fibers at least one composition T, the composition comprising at least one anionic surfactant and / or at least one amphoteric or zwitterionic surfactant and less than 1% by weight of silicone relative to the total weight of composition T; and then b) applying to the keratinous hair fibers at least one composition C, the composition comprising: - at least one (poly)carbodiimide compound; and - at least one colorant selected from pigments, direct dyes, and mixtures thereof, wherein the (poly)carbodiimide compound is selected from compounds of the following formula (II): wherein: - X1 and X2 independently represent an oxygen atom O, a sulfur atom S, or an NH group; - R1 and R2 independently represent a hydrocarbon-based group optionally interrupted by one or more heteroatoms; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w indicates an integer ranging from 1 to 3; -L1 independently represents C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkanediyl group, C3-C 12 a heterocycloalkanediyl group or C6-C 14 an arylene group, and mixtures thereof; - E independently represents a group selected from: - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; where R3 and R4 independently represent a divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; - R5 independently represents a covalent bond or a saturated divalent hydrocarbon-based group optionally interrupted by one or more heteroatoms; - R6 independently represents a hydrogen atom or a hydrocarbon-based group optionally interrupted by one or more heteroatoms.

2. The method according to claim 1, wherein The anionic surfactant is selected from sulfate-based anionic surfactants.

3. The method according to claim 1 or 2, characterized in that, The anionic surfactant is present in a total content ranging from 1% to 50% by weight, preferably from 5% to 40% by weight, more preferably from 10% to 30% by weight, and even more preferably from 12% to 20% by weight relative to the total weight of composition T.

4. The method according to any one of the preceding claims, characterized in that, The zwitterionic or amphoteric surfactant is selected from (C8-C 20 ) alkyl betaines, (C8-C 20 ) alkyl sulfobetaines, (C8-C 20 ) alkylamido (C3-C8) alkyl betaines, (C8-C 20 ) alkylamido (C6-C8) alkyl sulfobetaines, and mixtures thereof, more preferably selected from (C8-C 20 ) alkyl betaines, (C8-C 20 ) alkylamido (C3-C8) alkyl betaines, and mixtures thereof, and even more preferably selected from (C8-C 20 ) alkylamido (C3-C8) alkyl betaines, and mixtures thereof.

5. The method according to any one of the preceding claims, characterized in that, The amphoteric or zwitterionic surfactant is present in a total content ranging from 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.75% to 15% by weight, even more preferably from 1% to 10% by weight, and still better from 1.2% to 5% by weight relative to the total weight of composition T.

6. The method according to any one of the preceding claims, characterized in that, Composition T is free of silicone.

7. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II) wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently are selected from dialkylamino alcohols, alkyl esters of hydroxycarboxylic acids, and monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl group has been removed, and mixtures thereof; - n and z indicate integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1; -L1 is selected from C1-C 18 a divalent aliphatic hydrocarbon-based group, C3-C 15 a cycloalkylene group, C3-C 12 a heterocycloalkylene group or C6-C 14 an arylene group, and mixtures thereof; - E independently represents a group selected from: - O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, straight-chain or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

8. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from compounds of formula (II) wherein: - X1 and X2 independently represent an oxygen atom; - R1 and R2 independently are monoalkyl ethers of (poly)alkylene glycols from which the hydroxyl group has been removed; -n and z denote integers ranging from 1 to 20, where n + z ≥ 2 and w equals 1; -L1 is C3-C 15 subcycloalkyl; -E independently represents a group selected from: -O-R3-O-; -S-R4-S-; -R5-N(R6)-R4-N(R6)-R5-; wherein R3 and R4 are independently selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; - When R5 is not a covalent bond, R5 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof; and -R6 is selected from C6-C optionally inserted with one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

9. The method according to any one of the preceding claims, characterized in that The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently represent a compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; -n and z denote integers ranging from 1 to 20, where the range of n + z is from 4 to 10 and w equals 1; -L1 is a C3-C 15 subcycloalkyl group such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 is selected from C6-C optionally interrupted by one or more heteroatoms 14 arylene, C3-C 12 cycloalkylene, linear or branched C1-C 18 alkylene, and mixtures thereof.

10. The method according to any one of the preceding claims, characterized in that The (poly)carbodiimide compound is selected from the compounds of formula (II), wherein: -X1 and X2 independently represent an oxygen atom; -R1 and R2 independently represent the compound of the following formula (VI): R 13 -[O-CH2-C(H)(R 14 )] q -(VI), wherein R 13 represents a C1-C4 alkyl or phenyl group, preferably a C1-C4 alkyl group, more preferably a methyl group, and R 14 represents a hydrogen atom or a C1-C4 alkyl group, preferably a hydrogen atom, and q indicates an integer ranging from 4 to 30; -n and z denote integers ranging from 1 to 20, where the range of n + z is from 4 to 10 and w equals 1; -L1 is a C3-C 15 subcycloalkyl group such as cyclopentylene, cycloheptylene, cyclohexylene and 4,4-dicyclohexylmethane, preferably 4,4-dicyclohexylmethane; and -E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene.

11. The method according to any one of the preceding claims, characterized in that, The (poly)carbodiimide compound is selected from the compounds of formula (XII): wherein L1 is 4,4'-dicyclohexylmethane, n and z denote integers ranging from 1 to 20, where the range of n + z is from 4 to 10, E represents the group -O-R3-O-, where R3 represents a straight-chain or branched C1-C 18 alkylene group, such as methylene, propylene, butylene or ethylene, and r and s denote integers ranging from 4 to 30.

12. The method according to any one of the preceding claims, characterized in that The total amount of the (poly)carbodiimide compound ranges from 0.01% to 20% by weight, preferably from 0.1% to 15% by weight, more preferably from 0.2% to 10% by weight, even more preferably from 0.5% to 8% by weight, and still better from 1% to 6% by weight, relative to the total weight of composition C.

13. The method according to any one of the preceding claims, characterized in that, The total amount of the colorant selected from pigments, direct dyes and mixtures thereof ranges from 0.001% to 20% by weight and preferably from 0.005% to 15% by weight, relative to the total weight of composition C.

14. The method according to any one of the preceding claims, characterized in that Step b) comprises instantaneously mixing at least two compositions A and B during use to obtain composition C and comprises applying composition C to the keratinous hair fibers, wherein: -Composition A contains at least one (poly)carbodiimide compound as defined in any one of claims 1 and 7 to 11; Composition A and / or composition B contains at least one colorant selected from pigments, direct dyes and mixtures thereof as defined in claim 1.

15. The method according to any one of the preceding claims, characterized in that, Composition C or composition B contains at least one compound containing at least one carboxyl functional group, which is preferably selected from silicone compounds containing at least one carboxyl group, polyurethanes, acrylic polymers and mixtures thereof.

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